Method for manufacturing fluoropolymer, surfactant for polymerization, use for surfactant, and composition

ABSTRACT

A method for producing a fluoropolymer which includes polymerizing a fluoromonomer in an aqueous medium in the presence of a surfactant to provide a fluoropolymer, the surfactant being represented by the general formula (1): CR 1 R 2 R 4 —CR 3 R 5 —X-A, wherein R 1  to R 5  are each H or a monovalent substituent, with the proviso that at least one of R 1  and R 3  represents a group represented by the general formula: —Y—R 6  and at least one of R 2  and R 5  represents a group represented by the general formula: —X-A or a group represented by the general formula: —Y—R 6 ; and A is the same or different at each occurrence and is —COOM, —SO 3 M, or —OSO 3 M. Also disclosed is a surfactant for polymerization represented by the general formula (1), a method for producing a fluoropolymer using the surfactant and a composition including a fluoropolymer and the surfactant.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Stage of International Application No.PCT/JP2019/004456 filed Feb. 7, 2019, claiming priority based onJapanese Patent Application No. 2018-020974 filed Feb. 8, 2018 andJapanese Patent Application No. 2019-014709 filed Jan. 30, 2019.

TECHNICAL FIELD

The present invention relates to a method for producing a fluoropolymer.The present invention also relates to a surfactant for polymerization.The present invention also relates to use of a surfactant for productionof a fluoropolymer. The present invention further relates to acomposition.

BACKGROUND ART

Fluorinated anion surfactants have been used in production offluoropolymers by emulsion polymerization. Recently, it has beenproposed to use hydrocarbon surfactants instead of the fluorinated anionsurfactants.

For example, Patent Document 1 discloses a semi-batch emulsionpolymerization process for the production of a fluoroelastomer, thefluoroelastomer having at least 58 weight percent fluorine, comprising:(A) charging a reactor with a quantity of an aqueous solutionsubstantially free from surfactant; (B) charging the reactor with aquantity of a monomer mixture containing i) from 25 to 75 weightpercent, based on total weight of the monomer mixture, of a firstmonomer, the first monomer selected from the group consisting ofvinylidene fluoride and tetrafluoroethylene, and ii) between 75 and 25weight percent, based on total weight of the monomer mixture, of one ormore additional copolymerizable monomers, different from the firstmonomer, wherein the additional monomer is selected from the groupconsisting of fluorine-containing olefins, fluorine-containing vinylethers, hydrocarbon olefins and mixtures thereof; (C) initiatingpolymerization to form a fluoroelastomer dispersion while maintainingthe reaction medium at a pH between 1 and 7, at a pressure between 0.5and 10 MPa, and at a temperature between 25° C. and 130° C.; and (D)charging the reactor, after polymerization has begun, with a quantity ofa hydrocarbon anionic surfactant of the formula R-L-M wherein R is analkyl group having between 6 and 17 carbon atoms, L is selected from thegroup consisting of —ArSO₃—, —SO₃—, —SO₄—, —PO₃—, and —COO— and M is aunivalent cation.

RELATED ART Patent Documents

Patent Document 1: National Publication of International PatentApplication No. 2010-511096

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

An object of the present invention is to provide a novel method forproducing a fluoropolymer.

Means for Solving the Problem

The present invention relates to a method for producing a fluoropolymercomprising polymerizing a fluoromonomer in an aqueous medium in thepresence of a surfactant to provide a fluoropolymer, the surfactantbeing represented by the following general formula (1):

wherein R¹ to R⁵ each represent H or a monovalent substituent, with theproviso that at least one of R¹ and R³ represents a group represented bythe general formula: —Y—R⁶ and at least one of R² and R⁵ represents agroup represented by the general formula: —X-A or a group represented bythe general formula: —Y—R⁶;

X is the same or different at each occurrence and represents a divalentlinking group or a direct bond;

A is the same or different at each occurrence and represents —COOM,—SO₃M, or —OSO₃M, wherein M is H, a metal atom, NR⁷ ₄, imidazoliumoptionally having a substituent, pyridinium optionally having asubstituent, or phosphonium optionally having a substituent, wherein R⁷is H or an organic group;

Y is the same or different at each occurrence and represents a divalentlinking group selected from the group consisting of —S(═O)₂—, —O—,—COO—, —OCO—, —CONR⁸—, and —NR⁸CO—, or a direct bond, wherein R⁸ is H oran organic group;

R⁶ is the same or different at each occurrence and represents an alkylgroup having 2 or more carbon atoms and optionally containing, betweencarbon atoms, at least one selected from the group consisting of acarbonyl group, an ester group, an amide group, and a sulfonyl group;and

any two of R¹ to R⁵ optionally bind to each other to form a ring.

The surfactant is preferably a compound represented by the generalformula (1-1) or a compound represented by the general formula (1-2):

General Formula (1-1):

wherein R³ to R⁶, X, A, and Y are defined as described above.

General Formula (1-2):

wherein R⁴ to R⁶, X, A, and Y are defined as described above.

In the general formula (1), R⁴ and R⁵ are preferably each H or a C₁₋₄alkyl group.

In the general formula (1), M is preferably H, Na, K, Li, or NH₄.

In the general formula (1), M is preferably Na, K, or NH₄.

In the general formula (1), M is preferably NH₄.

The polymerization of the fluoromonomer is preferably performed in theabsence of a fluorine-containing surfactant.

The present invention also relates to a surfactant for polymerizationrepresented by the following general formula (1):

wherein R¹ to R⁵ each represent H or a monovalent substituent, with theproviso that at least one of R¹ and R³ represents a group represented bythe general formula: —Y—R⁶ and at least one of R² and R⁵ represents agroup represented by the general formula: —X-A or a group represented bythe general formula: —Y—R⁶;

X is the same or different at each occurrence and represents a divalentlinking group or a direct bond; A is the same or different at eachoccurrence and represents —COOM, —SO₃M, or —OSO₃M, wherein M is H, ametal atom, NR⁷ ₄, imidazolium optionally having a substituent,pyridinium optionally having a substituent, or phosphonium optionallyhaving a substituent, wherein R⁷ is H or an organic group;

Y is the same or different at each occurrence and represents a divalentlinking group selected from the group consisting of —S(═O)₂—, —O—,—COO—, —OCO—, —CONR⁸—, and —NR⁸CO—, or a direct bond, wherein R⁸ is H oran organic group;

R⁶ is the same or different at each occurrence and represents an alkylgroup having 2 or more carbon atoms and optionally containing, betweencarbon atoms, at least one selected from the group consisting of acarbonyl group, an ester group, an amide group, and a sulfonyl group;and

any two of R¹ to R⁵ optionally bind to each other to form a ring.

The present invention also relates to use of a surfactant for productionof a fluoropolymer by polymerizing a fluoromonomer in an aqueous medium,the surfactant being represented by the following general formula (1):

wherein R¹ to R⁵ each represent H or a monovalent substituent, with theproviso that at least one of R¹ and R³ represents a group represented bythe general formula: —Y—R⁶ and at least one of R² and R⁵ represents agroup represented by the general formula: —X-A or a group represented bythe general formula: —Y—R⁶;

X is the same or different at each occurrence and represents a divalentlinking group or a direct bond;

A is the same or different at each occurrence and represents —COOM,—SO₃M, or —OSO₃M, wherein M is H, a metal atom, NR⁷ ₄, imidazoliumoptionally having a substituent, pyridinium optionally having asubstituent, or phosphonium optionally having a substituent, wherein R⁷is H or an organic group;

Y is the same or different at each occurrence and represents a divalentlinking group selected from the group consisting of —S(═O)₂—, —O—,—COO—, —OCO—, —CONR⁸—, and —NR⁸CO—, or a direct bond, wherein R⁸ is H oran organic group;

R⁶ is the same or different at each occurrence and represents an alkylgroup having 2 or more carbon atoms and optionally containing, betweencarbon atoms, at least one selected from the group consisting of acarbonyl group, an ester group, an amide group, and a sulfonyl group;and

any two of R¹ to R⁵ optionally bind to each other to form a ring.

The present invention also relates to a composition comprising afluoropolymer and a surfactant represented by the following generalformula (1):

wherein R¹ to R⁵ each represent H or a monovalent substituent, with theproviso that at least one of R¹ and R³ represents a group represented bythe general formula: —Y—R⁶ and at least one of R² and R⁵ represents agroup represented by the general formula: —X-A or a group represented bythe general formula: —Y—R⁶;

X is the same or different at each occurrence and represents a divalentlinking group or a direct bond;

A is the same or different at each occurrence and represents —COOM,—SO₃M, or —OSO₃M, wherein M is H, a metal atom, NR⁷ ₄, imidazoliumoptionally having a substituent, pyridinium optionally having asubstituent, or phosphonium optionally having a substituent, wherein

R⁷ is H or an organic group; Y is the same or different at eachoccurrence and represents a divalent linking group selected from thegroup consisting of —S(═O)₂—, —O—, —COO—, —OCO—, —CONR⁸—, and —NR⁸CO—,or a direct bond, wherein R⁸ is H or an organic group;

R⁶ is the same or different at each occurrence and represents an alkylgroup having 2 or more carbon atoms and optionally containing, betweencarbon atoms, at least one selected from the group consisting of acarbonyl group, an ester group, an amide group, and a sulfonyl group;and

any two of R¹ to R⁵ optionally bind to each other to form a ring.

The composition of the present invention is preferably substantiallyfree from a fluorine-containing surfactant.

In the composition of the present invention, in the general formula (1),A is preferably —COOM. In the general formula (1), at least one of R²and R⁵ is a group represented by the general formula: —X-A, and A ispreferably —COOM.

The composition of the present invention is preferably a powder.

The present invention further relates to a molded body comprising thecomposition.

Effects of Invention

The production method of the present invention is a novel method forproducing a fluoropolymer.

According to the production method of the present invention, thepolymerization is carried out in the presence of the surfactant, so thata fluoropolymer having a high molecular weight can be produced, and thesurfactant is less likely to remain in the resulting fluoropolymer.

DESCRIPTION OF EMBODIMENTS

Before describing the present invention in detail, some terms usedherein are defined or described below.

The fluororesin as used herein means a partially crystallinefluoropolymer which is a fluoroplastic. The fluororesin has a meltingpoint and has thermoplasticity, and may be either melt-fabricable or nonmelt-processible.

The melt-fabricable as used herein means that a polymer has an abilityto be processed in a molten state using a conventional processing devicesuch as an extruder or an injection molding machine. Thus, amelt-fabricable fluororesin usually has a melt flow rate of 0.01 to 500g/10 min as measured by the measurement method to be described later.

The fluoroelastomer as used herein means an amorphous fluoropolymer. Theterm “amorphous” means that a fluoropolymer has a melting peak (ΔH) of4.5 J/g or lower as determined by differential scanning calorimetry(DSC) (temperature-increasing rate: 10° C./min) or differential thermalanalysis (DTA) (temperature-increasing rate: 10° C./min). Thefluoroelastomer exhibits elastomeric characteristics when crosslinked.The elastomeric characteristics mean that a polymer has an ability to bestretched and to retain its original length when the force required tostretch the polymer is no longer applied.

The partially fluorinated elastomer as used herein means a fluoropolymercontaining a fluoromonomer unit, having a perfluoromonomer unit contentof less than 90 mol % based on all polymerized units, having a glasstransition temperature of 20° C. or lower, and having a melting peak(ΔH) of 4.5 J/g or lower.

The perfluoroelastomer as used herein means a fluoropolymer having aperfluoromonomer unit content of 90 mol % or more based on allpolymerized units, having a glass transition temperature of 20° C. orlower, having a melting peak (ΔH) of 4.5 J/g or lower, and having afluorine atom concentration in the fluoropolymer of 71% by mass or more.The fluorine atom concentration in the fluoropolymer as used herein isthe concentration (% by mass) of the fluorine atoms contained in thefluoropolymer calculated based on the type and content of each monomerconstituting the fluoropolymer.

The perfluoromonomer as used herein means a monomer free from acarbon-hydrogen bond in the molecule. The perfluoromonomer may be amonomer containing carbon atoms and fluorine atoms in which some of thefluorine atoms bonded to any of the carbon atoms are replaced bychlorine atoms, and may be a monomer containing a nitrogen atom, anoxygen atom, a sulfur atom, a phosphorus atom, a boron atom, or asilicon atom in addition to the carbon atoms. The perfluoromonomer ispreferably a monomer in which all hydrogen atoms are replaced byfluorine atoms. The perfluoromonomer does not encompass a monomer thatprovides a crosslinking site.

The monomer that provides a crosslinking site is a monomer (cure-sitemonomer) having a crosslinkable group that provides the fluoropolymerwith a crosslinking site for forming a crosslink with the curing agent.

The polytetrafluoroethylene (PTFE) as used herein is preferably afluoropolymer having a tetrafluoroethylene content of 99 mol % or morebased on all polymerized units.

The fluororesin other than polytetrafluoroethylene and thefluoroelastomer as used herein are each preferably a fluoropolymerhaving a tetrafluoroethylene content of less than 99 mol % based on allpolymerized units.

The content of each monomer constituting the fluoropolymer can becalculated herein by any appropriate combination of NMR, FT-IR,elemental analysis, and X-ray fluorescence analysis in accordance withthe type of the monomer.

The term “organic group” as used herein means a group containing one ormore carbon atoms or a group obtainable by removing one hydrogen atomfrom an organic compound.

Examples of the “organic group” include:

an alkyl group optionally having one or more substituents,

an alkenyl group optionally having one or more substituents,

an alkynyl group optionally having one or more substituents,

a cycloalkyl group optionally having one or more substituents,

a cycloalkenyl group optionally having one or more substituents,

a cycloalkadienyl group optionally having one or more substituents,

an aryl group optionally having one or more substituents,

an aralkyl group optionally having one or more substituents,

a non-aromatic heterocyclic group optionally having one or moresubstituents,

a heteroaryl group optionally having one or more substituents,

a cyano group,

a formyl group,

RaO—,

RaCO—,

RaSO₂—,

RaCOO—,

RaNRaCO—,

RaCONRa—,

RaOCO—,

RaOSO₂—, and

RaNRbSO₂—,

wherein each Ra is independently

an alkyl group optionally having one or more substituents,

an alkenyl group optionally having one or more substituents,

an alkynyl group optionally having one or more substituents,

a cycloalkyl group optionally having one or more substituents,

a cycloalkenyl group optionally having one or more substituents,

a cycloalkadienyl group optionally having one or more substituents,

an aryl group optionally having one or more substituents,

an aralkyl group optionally having one or more substituents,

a non-aromatic heterocyclic group optionally having one or moresubstituents, or

a heteroaryl group optionally having one or more substituents, and

each Rb is independently H or an alkyl group optionally having one ormore substituents.

The organic group is preferably an alkyl group optionally having one ormore substituents.

The term “substituent” as used herein means a group capable of replacinganother atom or group. Examples of the “substituent” include analiphatic group, an aromatic group, a heterocyclic group, an acyl group,an acyloxy group, an acylamino group, an aliphatic oxy group, anaromatic oxy group, a heterocyclic oxy group, an aliphatic oxycarbonylgroup, an aromatic oxycarbonyl group, a heterocyclic oxycarbonyl group,a carbamoyl group, an aliphatic sulfonyl group, an aromatic sulfonylgroup, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, anaromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, asulfamoyl group, an aliphatic sulfonamide group, an aromatic sulfonamidegroup, a heterocyclic sulfonamide group, an amino group, an aliphaticamino group, an aromatic amino group, a heterocyclic amino group, analiphatic oxycarbonylamino group, an aromatic oxycarbonylamino group, aheterocyclic oxycarbonylamino group, an aliphatic sulfinyl group, anaromatic sulfinyl group, an aliphatic thio group, an aromatic thiogroup, a hydroxy group, a cyano group, a sulfo group, a carboxy group,an aliphatic oxyamino group, an aromatic oxyamino group, acarbamoylamino group, a sulfamoyl amino group, a halogen atom, asulfamoyl carbamoyl group, a carbamoyl sulfamoyl group, a dialiphaticoxyphosphinyl group, and a diaromatic oxyphosphinyl group.

The aliphatic group may be saturated or unsaturated, and may have ahydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphaticoxycarbonyl group, an aliphatic thio group, an amino group, an aliphaticamino group, an acylamino group, a carbamoylamino group, or the like.Examples of the aliphatic group include alkyl groups having 1 to 8,preferably 1 to 4 carbon atoms in total, such as a methyl group, anethyl group, a vinyl group, a cyclohexyl group, and a carbamoylmethylgroup.

The aromatic group may have, for example, a nitro group, a halogen atom,an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonylgroup, an aliphatic thio group, an amino group, an aliphatic aminogroup, an acylamino group, a carbamoylamino group, or the like. Examplesof the aromatic group include aryl groups having 6 to 12 carbon atoms,preferably 6 to 10 carbon atoms in total, such as a phenyl group, a4-nitrophenyl group, a 4-acetylaminophenyl group, and a4-methanesulfonylphenyl group.

The heterocyclic group may have a halogen atom, a hydroxy group, analiphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group,an aliphatic thio group, an amino group, an aliphatic amino group, anacylamino group, a carbamoylamino group, or the like. Examples of theheterocyclic group include 5- or 6-membered heterocyclic groups having 2to 12, preferably 2 to 10 carbon atoms in total, such as a2-tetrahydrofuryl group and a 2-pyrimidyl group.

The acyl group may have an aliphatic carbonyl group, an arylcarbonylgroup, a heterocyclic carbonyl group, a hydroxy group, a halogen atom,an aromatic group, an aliphatic oxy group, a carbamoyl group, analiphatic oxycarbonyl group, an aliphatic thio group, an amino group, analiphatic amino group, an acylamino group, a carbamoylamino group, orthe like. Examples of the acyl group include acyl groups having 2 to 8,preferably 2 to 4 carbon atoms in total, such as an acetyl group, apropanoyl group, a benzoyl group, and a 3-pyridinecarbonyl group.

The acylamino group may have an aliphatic group, an aromatic group, aheterocyclic group, or the like, and may have, for example, anacetylamino group, a benzoylamino group, a 2-pyridinecarbonylaminogroup, a propanoylamino group, or the like. Examples of the acylaminogroup include acylamino groups having 2 to 12, preferably 2 to 8 carbonatoms in total, and alkylcarbonylamino groups having 2 to 8 carbon atomsin total, such as an acetylamino group, a benzoylamino group, a2-pyridinecarbonylamino group, and a propanoylamino group.

The aliphatic oxycarbonyl group may be saturated or unsaturated, and mayhave a hydroxy group, an aliphatic oxy group, a carbamoyl group, analiphatic oxycarbonyl group, an aliphatic thio group, an amino group, analiphatic amino group, an acylamino group, a carbamoylamino group, orthe like. Examples of the aliphatic oxycarbonyl group includealkoxycarbonyl groups having 2 to 8, preferably 2 to 4 carbon atoms intotal, such as a methoxycarbonyl group, an ethoxycarbonyl group, and a(t)-butoxycarbonyl group.

The carbamoyl group may have an aliphatic group, an aromatic group, aheterocyclic group, or the like. Examples of the carbamoyl group includean unsubstituted carbamoyl group and alkylcarbamoyl groups having 2 to 9carbon atoms in total, preferably an unsubstituted carbamoyl group andalkylcarbamoyl groups having 2 to 5 carbon atoms in total, such as aN-methylcarbamoyl group, a N,N-dimethylcarbamoyl group, and aN-phenylcarbamoyl group.

The aliphatic sulfonyl group may be saturated or unsaturated, and mayhave a hydroxy group, an aromatic group, an aliphatic oxy group, acarbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiogroup, an amino group, an aliphatic amino group, an acylamino group, acarbamoylamino group, or the like. Examples of the aliphatic sulfonylgroup include alkylsulfonyl groups having 1 to 6 carbon atoms in total,preferably 1 to 4 carbon atoms in total, such as methanesulfonyl.

The aromatic sulfonyl group may have a hydroxy group, an aliphaticgroup, an aliphatic oxy group, a carbamoyl group, an aliphaticoxycarbonyl group, an aliphatic thio group, an amino group, an aliphaticamino group, an acylamino group, a carbamoylamino group, or the like.Examples of the aromatic sulfonyl group include arylsulfonyl groupshaving 6 to 10 carbon atoms in total, such as a benzenesulfonyl group.

The amino group may have an aliphatic group, an aromatic group, aheterocyclic group, or the like.

The acylamino group may have, for example, an acetylamino group, abenzoylamino group, a 2-pyridinecarbonylamino group, a propanoylaminogroup, or the like. Examples of the acylamino group include acylaminogroups having 2 to 12 carbon atoms in total, preferably 2 to 8 carbonatoms in total, and more preferably alkylcarbonylamino groups having 2to 8 carbon atoms in total, such as an acetylamino group, a benzoylaminogroup, a 2-pyridinecarbonylamino group, and a propanoylamino group.

The aliphatic sulfonamide group, aromatic sulfonamide group, andheterocyclic sulfonamide group may be, for example, a methanesulfonamidegroup, a benzenesulfonamide group, a 2-pyridinesulfonamide group,respectively.

The sulfamoyl group may have an aliphatic group, an aromatic group, aheterocyclic group, or the like. Examples of the sulfamoyl group includea sulfamoyl group, alkylsulfamoyl groups having 1 to 9 carbon atoms intotal, dialkylsulfamoyl groups having 2 to 10 carbon atoms in total,arylsulfamoyl groups having 7 to 13 carbon atoms in total, andheterocyclic sulfamoyl groups having 2 to 12 carbon atoms in total, morepreferably a sulfamoyl group, alkylsulfamoyl groups having 1 to 7 carbonatoms in total, dialkylsulfamoyl groups having 3 to 6 carbon atoms intotal, arylsulfamoyl groups having 6 to 11 carbon atoms in total, andheterocyclic sulfamoyl groups having 2 to 10 carbon atoms in total, suchas a sulfamoyl group, a methylsulfamoyl group, a N,N-dimethylsulfamoylgroup, a phenylsulfamoyl group, and a 4-pyridinesulfamoyl group.

The aliphatic oxy group may be saturated or unsaturated, and may have amethoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxygroup, a methoxyethoxy group, or the like. Examples of the aliphatic oxygroup include alkoxy groups having 1 to 8, preferably 1 to 6 carbonatoms in total, such as a methoxy group, an ethoxy group, an i-propyloxygroup, a cyclohexyloxy group, and a methoxyethoxy group.

The aromatic amino group and the heterocyclic amino group each may havean aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoylgroup, a heterocyclic group ring-fused with the aryl group, and analiphatic oxycarbonyl group, preferably an aliphatic group having 1 to 4carbon atoms in total, an aliphatic oxy group having 1 to 4 carbon atomsin total, a halogen atom, a carbamoyl group having 1 to 4 carbon atomsin total, a nitro group, or an aliphatic oxycarbonyl group having 2 to 4carbon atoms in total.

The aliphatic thio group may be saturated or unsaturated, and examplesthereof include alkylthio groups having 1 to 8 carbon atoms in total,more preferably 1 to 6 carbon atoms in total, such as a methylthiogroup, an ethylthio group, a carbamoylmethylthio group, and at-butylthio group.

The carbamoylamino group may have an aliphatic group, an aryl group, aheterocyclic group or the like.

Examples of the carbamoylamino group include a carbamoylamino group,alkylcarbamoylamino groups having 2 to 9 carbon atoms in total,dialkylcarbamoylamino groups having 3 to 10 carbon atoms in total,arylcarbamoylamino groups having 7 to 13 carbon atoms in total, andheterocyclic carbamoylamino groups having 3 to 12 carbon atoms in total,preferably a carbamoylamino group, alkylcarbamoylamino groups having 2to 7 carbon atoms in total, dialkylcarbamoylamino groups having 3 to 6carbon atoms in total, arylcarbamoylamino groups having 7 to 11 carbonatoms in total, and heterocyclic carbamoylamino group having 3 to 10carbon atoms in total, such as a carbamoylamino group, amethylcarbamoylamino group, a N,N-dimethylcarbamoylamino group, aphenylcarbamoylamino group, and a 4-pyridinecarbamoylamino group.

The ranges expressed by the endpoints as used herein each include allnumerical values within the range (for example, the range of 1 to 10includes 1.4, 1.9, 2.33, 5.75, 9.98, and the like).

The phrase “at least one” as used herein includes all numerical valuesequal to or greater than 1 (e.g., at least 2, at least 4, at least 6, atleast 8, at least 10, at least 25, at least 50, at least 100, and thelike).

The present invention will be specifically described hereinbelow.

The production method of the present invention is a method for producinga fluoropolymer comprising polymerizing a fluoromonomer in an aqueousmedium in the presence of a surfactant to provide a fluoropolymer, thesurfactant used being a surfactant represented by the following generalformula (1):

wherein R¹ to R⁵ each represent H or a monovalent substituent, with theproviso that at least one of R¹ and R³ represents a group represented bythe general formula: —Y—R⁶ and at least one of R² and R⁵ represents agroup represented by the general formula: —X-A or a group represented bythe general formula: —Y—R⁶;

X is the same or different at each occurrence and represents a divalentlinking group or a direct bond;

A is the same or different at each occurrence and represents —COOM,—SO₃M, or —OSO₃M, wherein M is H, a metal atom, NR⁷ ₄, imidazoliumoptionally having a substituent, pyridinium optionally having asubstituent, or phosphonium optionally having a substituent, wherein R⁷is H or an organic group;

Y is the same or different at each occurrence and represents a divalentlinking group selected from the group consisting of —S(═O)₂—, —O—,—COO—, —OCO—, —CONR⁸—, and —NR⁸CO—, or a direct bond, wherein R⁸ is H oran organic group;

R⁶ is the same or different at each occurrence and represents an alkylgroup having 2 or more carbon atoms and optionally containing, betweencarbon atoms, at least one selected from the group consisting of acarbonyl group, an ester group, an amide group, and a sulfonyl group;and

any two of R¹ to R⁵ optionally bind to each other to form a ring.

The surfactant (1) is described below.

In the formula, R¹ to R⁵ each represent H or a monovalent substituent,with the proviso that at least one of R¹ and R³ represents a grouprepresented by the general formula: —Y—R⁶ and at least one of R² and R⁵represents a group represented by the general formula: —X-A or a grouprepresented by the general formula: —Y—R⁶. Any two of R¹ to R⁵optionally bind to each other to form a ring.

The substituent which may be contained in the alkyl group for R¹ ispreferably a halogen atom, a linear or branched alkyl group having 1 to10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or ahydroxy group, particularly preferably a methyl group or an ethyl group.

The alkyl group for R¹ is preferably free from a carbonyl group.

In the alkyl group, 75% or less of the hydrogen atoms bonded to thecarbon atoms may be replaced by halogen atoms, 50% or less thereof maybe replaced by halogen atoms, or 25% or less thereof may be replaced byhalogen atoms. The alkyl group is preferably a non-halogenated alkylgroup free from halogen atoms such as fluorine atoms and chlorine atoms.

The alkyl group preferably contains no substituent.

R¹ is preferably a linear or branched alkyl group having 1 to 10 carbonatoms and optionally having a substituent or a cyclic alkyl group having3 to 10 carbon atoms and optionally having a substituent, morepreferably a linear or branched alkyl group having 1 to 10 carbon atomsand free from a carbonyl group or a cyclic alkyl group having 3 to 10carbon atoms and free from a carbonyl group, still more preferably alinear or branched alkyl group having 1 to 10 carbon atoms and nothaving a substituent, further preferably a linear or branched alkylgroup having 1 to 3 carbon atoms and not having a substituent,particularly preferably a methyl group (—CH₃) or an ethyl group (—C₂H₅),and most preferably a methyl group (—CH₃).

The monovalent substituent is preferably a group represented by thegeneral formula: —Y—R⁶, a group represented by the general formula:—X-A, —H, and a C₁₋₂₀ alkyl group optionally having a substituent, —NH₂,—NHR⁹ (wherein R⁹ is an organic group), —OH, —COOR⁹ (wherein R⁹ is anorganic group) or —OR⁹ (wherein R⁹ is an organic group). The alkyl grouppreferably has 1 to 10 carbon atoms.

R⁹ is preferably a C₁₋₁₀ alkyl group or a C₁₋₁₀ alkylcarbonyl group,more preferably a C₁₋₄ alkyl group or a C₁₋₄ alkylcarbonyl group.

In the formula, X is the same or different at each occurrence andrepresents a divalent linking group or a direct bond.

When R⁶ does not contain any of a carbonyl group, an ester group, anamide group, and a sulfonyl group, X is preferably a divalent linkinggroup containing at least one selected from the group consisting of acarbonyl group, an ester group, an amide group, and a sulfonyl group.

X is preferably a divalent linking group containing at least one bondselected from the group consisting of —CO—, —S(═O)₂—, —O—, —COO—, —OCO—,—S(═O)₂—O—, —O—S(═O)₂—, —CONR^(B)—, and —NR⁸CO—, a C₁₋₁₀ alkylene group,or a direct bond. R⁸ represents H or an organic group.

R⁸ is preferably H or a C₁₋₁₀ organic group, more preferably H or a C₁₋₄organic group, and still more preferably H.

In the formula, A is the same or different at each occurrence andrepresents —COOM, —SO₃M, or —OSO₃M, wherein M is H, a metal atom, NR⁷ ₄,imidazolium optionally having a substituent, pyridinium optionallyhaving a substituent, or phosphonium optionally having a substituent,wherein R⁷ is H or an organic group, and four R⁷ are the same as ordifferent from each other. In a preferred embodiment, in the generalformula (1), A is —COOM.

R⁷ is preferably H or a C₁₋₁₀ organic group, more preferably H or a C₁₋₄organic group.

Examples of the metal atom include alkali metals (Group 1) and alkalineearth metals (Group 2), and preferred is Na, K, or Li.

M is preferably H, a metal atom, or NR⁷ ₄, more preferably H, an alkalimetal (Group 1), an alkaline earth metal (Group 2), or NR⁷ ₄, still morepreferably H, Na, K, Li, or NH₄, further preferably Na, K, or NH₄,particularly preferably Na or NH₄, and most preferably NH₄.

In the formula, Y is the same or different at each occurrence andrepresents a divalent linking group selected from the group consistingof —S(═O)₂—, —O—, —COO—, —OCO—, —CONR^(B)—, and —NR⁸CO—, or a directbond, wherein R⁸ represents H or an organic group.

Y is preferably a divalent linking group selected from the groupconsisting of a direct bond, —O—, —COO—, —OCO—, —CONR^(B)—, and —NR⁸CO—,more preferably a divalent linking group selected from the groupconsisting of a direct bond, —COO—, and —OCO—.

R⁸ is preferably H or a C₁₋₁₀ organic group, more preferably H or a C₁₋₄organic group, and still more preferably H.

In the formula, R⁶ is the same or different at each occurrence andrepresents an alkyl group having 2 or more carbon atoms and optionallycontaining, between carbon atoms, at least one selected from the groupconsisting of a carbonyl group, an ester group, an amide group, and asulfonyl group. The organic group represented by R⁶ preferably has 2 to20 carbon atoms, more preferably 2 to 10 carbon atoms.

The alkyl group for R⁶ optionally contains, between carbon atoms, one ortwo or more of at least one selected from the group consisting of acarbonyl group, an ester group, an amide group, and a sulfonyl group,but the alkyl group contains no such groups at ends. In the alkyl groupfor R⁶, 75% or less of the hydrogen atoms bonded to the carbon atoms maybe replaced by halogen atoms, 50% or less thereof may be replaced byhalogen atoms, or 25% or less thereof may be replaced by halogen atoms.The alkyl group is preferably a non-halogenated alkyl group free fromhalogen atoms such as fluorine atoms and chlorine atoms.

R⁶ is preferably

a group represented by the general formula: —R¹⁰—CO—R¹¹,

a group represented by the general formula: —R¹⁰—COO—R¹¹,

a group represented by the general formula: —R¹¹,

a group represented by the general formula: —R¹⁰—NR⁸CO—R¹¹, or

a group represented by the general formula: —R¹⁰—CONR⁸—R¹¹,

wherein R⁸ represents H or an organic group; R¹⁰ represents an alkylenegroup; and R¹¹ represents an alkyl group optionally having asubstituent.

R⁶ is more preferably a group represented by the general formula:—R¹⁰—CO—R¹¹.

R⁸ is preferably H or a C₁₋₁₀ organic group, more preferably H or a C₁₋₄organic group, and still more preferably H.

The alkylene group for R¹⁰ preferably has 1 or more, and more preferably3 or more carbon atoms, and preferably 20 or less, more preferably 12 orless, still more preferably 10 or less, and particularly preferably 8 orless carbon atoms. Further, the alkylene group for R¹⁰ preferably has 1to 20, more preferably 1 to 10, and still more preferably 3 to 10 carbonatoms.

The alkyl group for R¹¹ may have 1 to 20 carbon atoms, and preferablyhas 1 to 15, more preferably 1 to 12, still more preferably 1 to 10,further preferably 1 to 8, still further preferably 1 to 6, still muchmore preferably 1 to 3, particularly preferably 1 or 2, and mostpreferably 1 carbon atom. The alkyl group for R¹¹ preferably consistsonly of primary carbons, secondary carbons, and tertiary carbons, andparticularly preferably consists only of primary carbons and secondarycarbons. In other words, R¹¹ is preferably a methyl group, an ethylgroup, an n-propyl group, or an isopropyl group, and most preferably amethyl group.

In a preferred embodiment, in the general formula (1), at least one ofR² and R⁵ is a group represented by the general formula: —X-A, and A ispreferably —COOM.

The surfactant (1) is preferably a compound represented by the generalformula (1-1), a compound represented by the general formula (1-2), or acompound represented by the general formula (1-3), more preferably acompound represented by the general formula (1-1) or a compoundrepresented by the general formula (1-2).

General Formula (1-1):

wherein R³ to R⁶, X, A, and Y are defined as described above.

General Formula (1-2):

wherein R⁴ to R⁶, X, A, and Y are defined as described above.

General formula (1-3):

wherein R², R⁴ to R⁶, X, A, and Y are defined as described above.

The group represented by the general formula: —X-A is preferably

—COOM,

—R¹²COOM,

—SO₃M,

—OSO₃M,

—R¹²SO₃M,

—R¹²OSO₃M,

—OCO—R¹²—COOM,

—OCO—R¹²—SO₃M,

—OCO—R¹²—OSO₃M

—COO—R¹²—COOM,

—COO—R¹²—SO₃M,

—COO—R¹²—OSO₃M,

—CONR⁸—R¹²—COOM,

—CONR⁸—R¹²—SO₃M,

—CONR⁸—R¹²—OSO₃M,

—NR⁸CO—R¹²—COOM,

—NR⁸CO—R¹²—SO₃M,

—NR⁸CO—R¹²—OSO₃M,

—OS(═O)₂—R¹²—COOM,

—OS(═O)₂—R¹²—SO₃M, or

—OS(═O)₂—R¹²—OSO₃M,

wherein R⁸ and M are defined as described above; and R¹² is a C₁₋₁₀alkylene group.

In the alkylene group for R¹², 75% or less of the hydrogen atoms bondedto the carbon atoms may be replaced by halogen atoms, 50% or lessthereof may be replaced by halogen atoms, or 25% or less thereof may bereplaced by halogen atoms. The alkylene group is preferably anon-halogenated alkylene group free from halogen atoms such as fluorineatoms and chlorine atoms.

The group represented by the general formula: —Y—R⁶ is preferably

a group represented by the general formula: —R¹⁰—CO—R¹¹,

a group represented by the general formula: —OCO—R¹⁰—CO—R¹¹,

a group represented by the general formula: —COO—R¹⁰—CO—R¹¹,

a group represented by the general formula: —OCO—R¹⁰—COO—R¹¹,

a group represented by the general formula: —COO—R¹¹,

a group represented by the general formula: —NR⁸CO—R¹⁰—CO—R¹¹, or

a group represented by the general formula: —CONR⁸—R¹⁰—NR⁸CO—R¹¹,wherein R⁸, R¹⁰, and R¹¹ are defined as described above.

In the formula, R⁴ and R⁵ are each independently preferably H or a C₁₋₄alkyl group.

In the alkyl groups for R⁴ and R⁵, 75% or less of the hydrogen atomsbonded to the carbon atoms may be replaced by halogen atoms, 50% or lessthereof may be replaced by halogen atoms, or 25% or less thereof may bereplaced by halogen atoms. The alkyl group is preferably anon-halogenated alkyl group free from halogen atoms such as fluorineatoms and chlorine atoms.

R³ in the general formula (1-1) is preferably H or a C₁₋₂₀ alkyl groupoptionally having a substituent, more preferably H or a C₁₋₂₀ alkylgroup having no substituent, and still more preferably H.

In the alkyl group for R³, 75% or less of the hydrogen atoms bonded tothe carbon atoms may be replaced by halogen atoms, 50% or less thereofmay be replaced by halogen atoms, or 25% or less thereof may be replacedby halogen atoms. The alkyl group is preferably a non-halogenated alkylgroup free from halogen atoms such as fluorine atoms and chlorine atoms.

R² in the general formula (1-3) is preferably H, OH, or a C₁₋₂₀ alkylgroup optionally having a substituent, more preferably H, OH, or a C₁₋₂₀alkyl group having no substituent, and still more preferably H or OH.

In the alkyl group for R², 75% or less of the hydrogen atoms bonded tothe carbon atoms may be replaced by halogen atoms, 50% or less thereofmay be replaced by halogen atoms, or 25% or less thereof may be replacedby halogen atoms. The alkyl group is preferably a non-halogenated alkylgroup free from halogen atoms such as fluorine atoms and chlorine atoms.

The surfactant (1) may suitably be produced by a production methodincluding:

a step (11) of reacting a carboxylic acid represented by the formula:R⁶—COOH (wherein R⁶ is defined as mentioned above) and a halogenatingagent to provide a carboxylic acid halide represented by the formula:R⁶—COZ (wherein R⁶ is defined as mentioned above; and Z is a halogenatom); and

a step (12) of reacting the carboxylic acid halide and a compoundrepresented by the formula:

(wherein R³ to R⁵, X, and A are defined as described above; and Z¹¹ is—CH₂O—, —O—, or —NH—) to provide a compound (12) represented by theformula:

wherein R³ to R⁶, X, A, and Z¹¹ are defined as described above.

R³ in the formula for the above acid compound is preferably a grouprepresented by the general formula: —Z¹¹H (wherein Z¹¹ is defined asdescribed above) or —H. When R³ is a group represented by the generalformula: —Z¹¹H, this group reacts with the carboxylic acid halide in thestep (12) to generate a group represented by the general formula:—Z¹¹—CO—R⁶, wherein R⁶ and Z¹¹ are defined as described above.

Examples of the halogenating agent used in the step (11) include oxalylchloride, thionyl chloride, diethylaminosulfur trifluoride (DAST),Deoxo-Fluor, and 1,1,2,2-tetrafluoro-N,N-dimethylethylamine (TFEDMA).

Z is preferably F or Cl, more preferably Cl.

Regarding the reaction ratio between the carboxylic acid and thehalogenating agent in the step (11), the amount of the halogenatingagent is preferably 0.6 to 5.0 mol, and more preferably 0.8 to 2.0 mol,based on 1 mol of the carboxylic acid in consideration of theimprovement of the yield and the reduction of the waste. The amount ofthe halogenating agent is also preferably 0.5 to 10 mol, and morepreferably 0.6 to 5.0 mol.

The reaction in the step (11) may be performed in a solvent. Examples ofthe solvent include esters, ketones, aromatic hydrocarbons, ethers,nitrogen-containing polar organic compounds, halogenated hydrocarbons,nitriles, pyridines, and mixtures thereof.

Examples of the esters include ethyl acetate, butyl acetate, ethyleneglycol monomethyl ether acetate, and propylene glycol monomethyl etheracetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), of whichethyl acetate is preferred.

Examples of the ketones include acetone, methyl ethyl ketone, methylisobutyl ketone, cyclohexanone, and diacetone alcohol, of which acetoneis preferred.

Examples of the aromatic hydrocarbon include benzene, toluene, andxylene, of which benzene and toluene are preferred.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane,and diethylene glycol diethyl ether, of which diethyl ether andtetrahydrofuran are preferred.

Examples of the nitrogen-containing polar organic compound includeN,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone,2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, of whichN,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidoneare preferred.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, ofwhich dichloromethane and chloroform are preferred.

Examples of the nitrile include acetonitrile, propionitrile,butyronitrile, isobutyronitrile, and benzonitrile, of which acetonitrileis preferred.

The reaction temperature in the step (11) is preferably 0 to 150° C.,and more preferably 20 to 100° C. The reaction temperature is alsopreferably −78 to 150° C., and more preferably 0 to 100° C.

The reaction pressure in the step (11) is preferably 0 to 5 MPa, andmore preferably 0.1 to 1.0 MPa.

The reaction duration in the step (11) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

Regarding the reaction ratio between the carboxylic acid halide and theacid compound in the step (12), the amount of the acid compound ispreferably 0.5 to 10 mol, more preferably 0.6 to 5.0 mol, and still morepreferably 0.8 to 2.0 mol, based on 1 mol of the carboxylic acid halidein consideration of the improvement of the yield and the reduction ofthe waste.

The reaction in the step (12) is preferably performed in the presence ofan acid. Examples of the acid include sulfuric acid, methanesulfonicacid, and p-toluenesulfonic acid, of which sulfuric acid is preferred.

The amount of the acid used in the step (12) is preferably 0.0001 to 1.0mol, and more preferably 0.001 to 0.1 mol, based on 1 mol of thecarboxylic acid halide in consideration of the improvement of the yieldand the reduction of the waste. The amount of the acid is alsopreferably 0.00001 to 1.0 mol, and more preferably 0.00005 to 0.1 mol.

The reaction temperature in the step (12) is preferably 0 to 150° C.,and more preferably 20 to 100° C.

The reaction pressure in the step (12) is preferably 0 to 5 MPa, andmore preferably 0.1 to 1.0 MPa.

The reaction duration in the step (12) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

The surfactant (1) may also suitably be produced by a production methodincluding a step (21) of reacting a compound (20) represented by theformula:

(wherein R¹ to R⁵ are defined as described above; and Z¹¹ is —CH₂O—,—O—, or —NH—) and an acid anhydride represented by the formula:

(wherein n is an integer of 1 to 5) to provide a compound (21)represented by the formula:

wherein R to R⁵, Z¹¹, M, and n are defined as described above.

R² in the formula of the compound (20) is preferably a group representedby the general formula: —Z¹¹H (wherein Z¹¹ is defined as describedabove) or —H. When R² is a group represented by the general formula:—Z¹¹H, this group reacts with the acid anhydride in the step (21) togenerate a group represented by the general formula:—Z¹¹—CO—(CH₂)_(n)—COOM, wherein Z¹¹, M, and n are defined as describedabove. The compound (20) may be a hydrochloride salt, a sulfate salt, orthe like as long as it has a structure represented by the above formula.

Regarding the reaction ratio between the compound (20) and the acidanhydride in the step (21), the amount of the acid anhydride ispreferably 1.2 to 10 mol, and more preferably 1.6 to 4.0 mol, based on 1mol of the compound (20) in consideration of the improvement of theyield and the reduction of the waste. The amount of the acid anhydrideis also preferably 0.5 to 10 mol, and more preferably 0.6 to 5.0 mol.

The reaction in the step (21) may be performed in the presence of abase.

Examples of the base include amines, potassium hydroxide, sodiumhydroxide, and potassium carbonate.

Examples of the amines include tertiary amines such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine,and N,N,N′,N′-tetramethyl-1,8-naphthalenediamine, heteroaromatic aminessuch as pyridine, pyrrole, uracil, collidine, and lutidine, and cyclicamines such as 1,8-diaza-bicyclo[5.4.0]-7-undecene and1,5-diaza-bicyclo[4.3.0]-5-nonene, and pyridine or triethylamine ispreferred.

The reaction temperature in the step (21) is preferably 0 to 150° C.,and more preferably 20 to 80° C. The reaction temperature is alsopreferably −78 to 150° C., and more preferably 0 to 100° C.

The reaction pressure in the step (21) is preferably 0 to 5 MPa, andmore preferably 0.1 to 1 MPa.

The reaction duration in the step (21) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

The surfactant (1) may also suitably be produced by a production methodincluding:

a step (31) of reacting a tartaric acid ester represented by theformula:

(wherein R⁴ and R⁵ are defined as described above) and an aminerepresented by the formula: R⁶R⁸—NH (wherein R⁶ and R⁸ are defined asdescribed above) to provide a compound (31) represented by the formula:

(wherein R⁴ to R⁶ and R⁸ are defined as described above); and

a step (32) of reacting the compound (31) and a chlorosulfonic acidrepresented by the formula:

(wherein M is defined as described above) to provide a compound (32)represented by the formula:

wherein R⁴ to R⁶, R⁸, and M are defined as described above.

Regarding the reaction ratio between the tartaric acid ester and theamine in the step (31), the amount of the amine is preferably 0.5 to 10mol, more preferably 0.6 to 5.0 mol, still more preferably 1.2 to 5 mol,and particularly preferably 1.6 to 5.0 mol, based on 1 mol of thetartaric acid ester in consideration of the improvement of the yield andthe reduction of the waste.

The reaction in the step (31) may be performed in a solvent. The solventis preferably an organic solvent, more preferably an alcohol, an ether,a halogenated hydrocarbon, a nitrogen-containing polar organic compound,or a nitrile.

Examples of the alcohol include methanol, ethanol, 1-propanol, andisopropanol.

Examples of the ether include tetrahydrofuran, dioxane, and diethyleneglycol diethyl ether.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene.

Examples of the nitrogen-containing polar organic compound includeN,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone,2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, of whichN,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidoneare preferred.

Examples of the nitrile include acetonitrile, propionitrile,butyronitrile, isobutyronitrile, and benzonitrile.

The reaction temperature in the step (31) is preferably 0 to 150° C.,and more preferably 20 to 100° C.

The reaction pressure in the step (31) is preferably 0 to 5 MPa, andmore preferably 0.1 to 1 MPa.

The reaction duration in the step (31) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

Regarding the reaction ratio between the compound (31) and thechlorosulfonic acid in the step (32), the amount of the chlorosulfonicacid is preferably 1.0 to 50 mol, and more preferably 1.6 to 20 mol,based on 1 mol of the compound (31) in consideration of the improvementof the yield and the reduction of the waste.

The reaction in the step (32) is preferably performed in the presence ofa base. Examples of the base include alkali metal hydroxides, alkalineearth metal hydroxides, and amines, of which amines are preferred.

Examples of the amines in the step (32) include tertiary amines such astrimethylamine, triethylamine, tributylamine, N,N-dimethylaniline,dimethylbenzylamine, and N,N,N′,N′-tetramethyl-1,8-naphthalenediamine,heteroaromatic amines such as pyridine, pyrrole, uracil, collidine, andlutidine, and cyclic amines such as 1,8-diaza-bicyclo[5.4.0]-7-undeceneand 1,5-diaza-bicyclo[4.3.0]-5-nonene. Of these, triethylamine ispreferred.

The amount of the base used in the step (32) is preferably 0.1 to 50mol, and more preferably 1.0 to 20 mol, based on 1 mol of the compound(31) in consideration of the improvement of the yield and the reductionof the waste.

The reaction in the step (32) may be performed in a solvent. The solventis preferably an organic solvent, more preferably an aprotic polarsolvent, and still more preferably a nitrile, a halogenated hydrocarbon,dimethyl sulfoxide, sulfolane, a nitrogen-containing polar organiccompound, or an ether.

Examples of the nitrile include acetonitrile, propionitrile,butyronitrile, isobutyronitrile, and benzonitrile, of which acetonitrileis preferred.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, ofwhich dichloromethane and chloroform are preferred.

Examples of the nitrogen-containing polar organic compound includeN,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone,2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, of whichN,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidoneare preferred.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane,and diethylene glycol diethyl ether, of which diethyl ether ispreferred.

The reaction temperature in the step (32) is preferably −78 to 150° C.,more preferably −78 to 100° C., still more preferably −20 to 100° C.,and particularly preferably 10 to 50° C.

The reaction pressure in the step (32) is preferably 0 to 5 MPa, andmore preferably 0.1 to 1.0 Pa.

The reaction duration in the step (32) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

The surfactant (1) may also suitably be produced by a production methodincluding a step (41) of reacting an alcohol represented by the formula:

(wherein R¹ and R³ to R⁵ are defined as described above) and an acidanhydride represented by the formula:

(wherein n is an integer of 1 to 5) to provide a compound (41)represented by the formula:

wherein R¹, R³ to R⁵, M, and n are defined as described above.

Regarding the reaction ratio between the alcohol and the acid anhydridein the step (41), the amount of the acid anhydride is preferably 0.5 to10 mol, more preferably 0.6 to 4.0 mol, still more preferably 1.2 to 4.0mol, and particularly preferably 1.6 to 4.0 mol, based on 1 mol of thealcohol in consideration of the improvement of the yield and thereduction of the waste.

The reaction in the step (41) may be performed in the presence of abase.

Examples of the base include amines, potassium hydroxide, sodiumhydroxide, and potassium carbonate.

Examples of the amines include tertiary amines such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine,and N,N,N′,N′-tetramethyl-1,8-naphthalenediamine, heteroaromatic aminessuch as pyridine, pyrrole, uracil, collidine, and lutidine, and cyclicamines such as 1,8-diaza-bicyclo[5.4.0]-7-undecene and1,5-diaza-bicyclo[4.3.0]-5-nonene, and pyridine or triethylamine ispreferred.

The reaction temperature in the step (41) is preferably −78 to 150° C.,more preferably 0 to 150° C., still more preferably 0 to 100° C., andparticularly preferably 20 to 80° C.

The reaction pressure in the step (41) is preferably 0 to 5 MPa, andmore preferably 0.1 to 1 MPa.

The reaction duration in the step (41) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

The surfactant (1) may also suitably be produced by a production methodincluding:

a step (31) of reacting a tartaric acid ester represented by theformula:

(wherein R⁴ and R⁵ are defined as described above) and an aminerepresented by the formula: R⁶R⁸—NH (wherein R⁶ and R⁸ are defined asdescribed above) to provide a compound (31) represented by the formula:

(wherein R⁴ to R⁶ and R⁸ are defined as described above); and

a step (51) of reacting the compound (31) and an acid anhydriderepresented by the formula:

(wherein n is an integer of 1 to 5) to provide a compound (51)represented by the formula:

wherein R⁴ to R⁶, R⁸, M, and n are defined as described above.

Regarding the reaction ratio between the compound (31) and the acidanhydride in the step (51), the amount of the acid anhydride ispreferably 0.5 to 10 mol, more preferably 0.6 to 4.0 mol, still morepreferably 1.2 to 4.0 mol, and particularly preferably 1.6 to 4.0 mol,based on 1 mol of the compound (31) in consideration of the improvementof the yield and the reduction of the waste.

The reaction in the step (51) may be performed in the presence of abase.

Examples of the base include amines, potassium hydroxide, sodiumhydroxide, and potassium carbonate.

Examples of the amines include tertiary amines such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline, dimethylbenzylamine,and N,N,N′,N′-tetramethyl-1,8-naphthalenediamine, heteroaromatic aminessuch as pyridine, pyrrole, uracil, collidine, and lutidine, and cyclicamines such as 1,8-diaza-bicyclo[5.4.0]-7-undecene and1,5-diaza-bicyclo[4.3.0]-5-nonene, and pyridine or triethylamine ispreferred.

The reaction temperature in the step (51) is preferably −78 to 150° C.,more preferably 0 to 150° C., still more preferably 0 to 100° C., andparticularly preferably 20 to 80° C.

The reaction pressure in the step (51) is preferably 0 to 5 MPa, andmore preferably 0.1 to 1 MPa.

The reaction duration in the step (51) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

The surfactant (1) may also suitably be produced by a production methodincluding:

a step (61) of reacting an alcohol represented by the formula: R⁶—OH(wherein R⁶ is defined as mentioned above) and a fumaric acid halide toprovide a compound (61) represented by the formula:

(wherein R⁶ is defined as mentioned above); and

a step (62) of reacting the compound (61) and a sulfonating agent suchas sodium hydrogen sulfite to provide a compound (62) represented by theformula:

wherein R⁶ and X are defined as mentioned above.

Examples of the fumaric acid halide used in the step (61) includefumaryl chloride, fumaryl fluoride, and fumaryl bromide.

Regarding the reaction ratio between the alcohol and the fumaric acidhalide in the step (61), the amount of the fumaric acid halide ispreferably 0.1 to 10 mol, more preferably 0.1 to 2.0 mol, andparticularly preferably 0.2 to 0.7 mol, based on 1 mol of the alcohol inconsideration of the improvement of the yield and the reduction of thewaste.

The reaction in the step (61) may be performed in a solvent. Examples ofthe solvent include esters, ketones, aromatic hydrocarbons, ethers,nitrogen-containing polar organic compounds, halogenated hydrocarbons,nitriles, pyridines, and mixtures thereof.

Examples of the esters include ethyl acetate, butyl acetate, ethyleneglycol monomethyl ether acetate, and propylene glycol monomethyl etheracetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), of whichethyl acetate is preferred.

Examples of the ketones include acetone, methyl ethyl ketone, methylisobutyl ketone, cyclohexanone, and diacetone alcohol, of which acetoneis preferred.

Examples of the aromatic hydrocarbon include benzene, toluene, andxylene, of which benzene and toluene are preferred.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane,and diethylene glycol diethyl ether, of which diethyl ether andtetrahydrofuran are preferred.

Examples of the nitrogen-containing polar organic compound includeN,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone,2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, of whichN,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidoneare preferred.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, ofwhich dichloromethane and chloroform are preferred.

Examples of the nitrile include acetonitrile, propionitrile,butyronitrile, isobutyronitrile, and benzonitrile, of which acetonitrileis preferred.

The reaction temperature in the step (61) is preferably −78 to 200° C.,and more preferably −20 to 150° C.

The reaction pressure in the step (61) is preferably 0 to 5.0 MPa, andmore preferably 0.1 to 1.0 MPa.

The reaction duration in the step (61) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

In the step (62), the compound (61) containing a double bond undergoesaddition reaction with a sulfonating agent such as sodium hydrogensulfite to generate the compound (62).

Regarding the reaction ratio between the compound (61) and thesulfonating agent in the step (62), the amount of the sulfonating agentis preferably 0.5 to 20.0 mol, more preferably 0.6 to 10.0 mol, stillmore preferably 0.8 to 10.0 mol, and particularly preferably 1.2 to 10.0mol, based on 1 mol of the compound (61) in consideration of theimprovement of the yield and the reduction of the waste.

The step (62) may be performed in a solvent. The solvent is preferably awater-soluble solvent, such as water, an alcohol, an ether, or anitrile.

Examples of the alcohol include methanol, ethanol, 1-propanol, andisopropanol.

Examples of the ether include tetrahydrofuran, dioxane, and diethyleneglycol diethyl ether.

Examples of the nitrile include acetonitrile, propionitrile,butyronitrile, isobutyronitrile, and benzonitrile, of which acetonitrileis preferred.

The reaction temperature in the step (62) is preferably −78 to 200° C.,and more preferably −20 to 150° C.

The reaction pressure in the step (62) is preferably 0 to 5.0 MPa, andmore preferably 0.1 to 1.0 MPa.

The reaction duration in the step (62) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

The surfactant (1) may also suitably be produced by a production methodincluding a step (71) of sulfuric-esterifying a compound (70)represented by the formula:

(wherein R¹⁰, R¹¹, and Y are defined as described above) to provide acompound (71) represented by the formula:

wherein R¹⁰, R¹¹, and Y are defined as described above; and A¹⁰⁰ is —OHor —OSO₃M, wherein M is defined as described above.

The sulfuric-esterification in the step (71) may be performed byreacting the compound (70) and a sulfating reagent. Examples of thesulfating reagent include sulfur trioxide amine complexes such as asulfur trioxide pyridine complex, a sulfur trioxide trimethylaminecomplex, and a sulfur trioxide triethylamine complex, sulfur trioxideamide complexes such as a sulfur trioxide dimethylformamide complex,sulfuric acid-dicyclohexylcarbodiimide, chlorosulfuric acid,concentrated sulfuric acid, and sulfamic acid. The amount of thesulfating reagent used is preferably 0.5 to 10 mol, more preferably 0.5to 5 mol, and still more preferably 0.7 to 4 mol, based on 1 mol of thecompound (70). By adjusting the amount of the sulfating reagent used,one or both of the two —OH groups of the compound (20) can besulfuric-esterified.

The sulfuric-esterification in the step (71) may be performed in asolvent. The solvent is preferably an organic solvent, and examplesthereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons,pyridines, dimethyl sulfoxide, sulfolane, and nitriles.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane,and diethylene glycol diethyl ether, of which diethyl ether andtetrahydrofuran are preferred.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, ofwhich dichloromethane and chloroform are preferred.

Examples of the aromatic hydrocarbon include benzene, toluene, andxylene, of which benzene and toluene are preferred.

Examples of the nitrile include acetonitrile, propionitrile,butyronitrile, isobutyronitrile, and benzonitrile, of which acetonitrileis preferred.

The sulfuric-esterification temperature in the step (71) is preferably−78 to 200° C., and more preferably −20 to 150° C.

The sulfuric-esterification pressure in the step (71) is preferably 0 to10 MPa, and more preferably 0.1 to 5 MPa.

The sulfuric-esterification duration in the step (71) is preferably 0.1to 72 hours, and more preferably 0.1 to 48 hours.

The compound (70) may also be produced by a production method including:

a step (101) of hydroxylating a compound (100) represented by theformula:

(wherein R¹⁰ and Y are defined as described above; and R¹⁰⁰ is an alkylgroup) to provide a compound (101) represented by the formula:

(wherein R¹⁰, R¹⁰⁰, and Y are defined as described above); and

a step (102) of oxidizing the compound (101) to provide the compound(70).

The alkyl group for R¹⁰⁰ constitutes the aforementioned R¹¹ in the formof R¹⁰⁰—CH₂—.

The hydroxylation in the step (101) may be performed by a method (1) inwhich iron(II) phthalocyanine (Fe(Pc)) and sodium borohydride are causedto act on the compound (100) in an oxygen atmosphere or a method (2) inwhich isopinocampheylborane (IpcBH₂) is caused to act on the compound(100) and then the resulting intermediate (dialkyl borane) is oxidized.

In the method (1), iron(II) phthalocyanine may be used in a catalyticamount, and may be used in an amount of 0.001 to 1.2 mol based on 1 molof the compound (100).

In the method (1), sodium borohydride may be used in an amount of 0.5 to20 mol based on 1 mol of the compound (100).

The reaction in the method (1) may be performed in a solvent. Thesolvent is preferably an organic solvent, and examples thereof includeethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, andnitrogen-containing polar organic compounds.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane,and diethylene glycol diethyl ether, of which diethyl ether andtetrahydrofuran are preferred.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, ofwhich dichloromethane and chloroform are preferred.

Examples of the aromatic hydrocarbon include benzene, toluene, andxylene, of which benzene and toluene are preferred.

Examples of the nitrile include acetonitrile, propionitrile,butyronitrile, isobutyronitrile, and benzonitrile, of which acetonitrileis preferred.

Examples of the nitrogen-containing polar organic compound includeN,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone,2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, of whichN,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidoneare preferred.

The reaction temperature in the method (1) is preferably −78 to 200° C.,and more preferably 0 to 150° C.

The reaction pressure in the method (1) is preferably 0 to 5.0 MPa, andmore preferably 0.1 to 1.0 MPa.

The reaction duration in the method (1) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

In the method (2), isopinocampheylborane may be used in an amount of 0.1to 10.0 mol based on 1 mol of the compound (100).

The reaction of the compound (100) and isopinocampheylborane may beperformed in a solvent. The solvent is preferably an organic solvent,and examples thereof include ethers, halogenated hydrocarbons, andaromatic hydrocarbons.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane,and diethylene glycol diethyl ether, of which diethyl ether andtetrahydrofuran are preferred.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, ofwhich dichloromethane and chloroform are preferred.

Examples of the aromatic hydrocarbon include benzene, toluene, andxylene, of which benzene and toluene are preferred.

The temperature of the reaction of the compound (100) andisopinocampheylborane is preferably −78 to 200° C., and more preferably0 to 150° C.

The pressure of the reaction of the compound (100) andisopinocampheylborane is preferably 0 to 5.0 MPa, and more preferably0.1 to 1.0 MPa.

The duration of the reaction of the compound (100) andisopinocampheylborane is preferably 0.1 to 72 hours, and more preferably0.1 to 48 hours.

The oxidation in the method (2) may be performed by causing an oxidizingagent to act on the intermediate. An example of the oxidizing agent ishydrogen peroxide. The oxidizing agent may be used in an amount of 0.7to 10 mol based on 1 mol of the intermediate.

The oxidation in the method (2) may be performed in a solvent. Examplesof the solvent include water, methanol, and ethanol, of which water ispreferred.

The oxidation temperature in the method (2) is preferably −78 to 150°C., more preferably 0 to 100° C., and still more preferably 10 to 80° C.

The oxidation pressure in the method (2) is preferably 0 to 5.0 MPa, andmore preferably 0.1 to 1.0 MPa.

The oxidation duration in the method (2) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

Examples of the method of oxidizing the compound (101) in the step (102)include (a) a method of using Jones reagent (CrO₃/H₂SO₄) (Jonesoxidation), (b) a method of using Dess-Martin periodinane (DMP)(Dess-Martin oxidation), (c) a method of using pyridinium chlorochromate(PCC), (d) a method of causing a bleaching agent (about 5 to 6% aqueoussolution of NaOCl) to act in the presence of a nickel compound such asNiCl₂, and (e) a method of causing a hydrogen acceptor such as analdehyde and a ketone to act in the presence of an aluminum catalystsuch as Al(CH₃)₃ or Al[OCH(CH₃)₂]₃ (Oppenauer oxidation).

The oxidation in the step (102) may be performed in a solvent. Thesolvent is preferably water or an organic solvent, and examples thereofinclude water, ketones, ethers, halogenated hydrocarbons, aromatichydrocarbons, and nitriles.

Examples of the ketones include acetone, methyl ethyl ketone, methylisobutyl ketone, cyclohexanone, and diacetone alcohol, of which acetoneis preferred.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane,and diethylene glycol diethyl ether, of which diethyl ether andtetrahydrofuran are preferred.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, ofwhich dichloromethane and chloroform are preferred.

Examples of the aromatic hydrocarbon include benzene, toluene, andxylene, of which benzene and toluene are preferred.

Examples of the nitrile include acetonitrile, propionitrile,butyronitrile, isobutyronitrile, and benzonitrile, of which acetonitrileis preferred.

The oxidation temperature in the step (102) is preferably −78 to 200°C., and may appropriately be selected in accordance with the methodused.

The oxidation pressure in the step (102) is preferably 0 to 5.0 MPa, andmay appropriately be selected in accordance with the method used.

The oxidation duration in the step (102) is preferably 0.1 to 72 hours,and may appropriately be selected in accordance with the method used.

The compound (70) may also be produced by a production method includinga step (201) of ozonolyzing a compound (200) represented by the formula:

(wherein R¹⁰, R¹¹, and Y are defined as described above; and R¹⁰¹ is anorganic group) to provide the compound (70).

R¹⁰¹ is preferably an alkyl group having 1 to 20 carbon atoms. The fourR¹⁰¹s are the same as or different from each other.

The ozonolysis in the step (201) may be performed by causing ozone toact on the compound (200), followed by post-treatment with a reducingagent.

The ozone may be generated by dielectric barrier discharge in oxygengas.

Examples of the reducing agent used in the post-treatment include zinc,dimethyl sulfide, thiourea, and phosphines, of which phosphines arepreferred.

The ozonolysis in the step (201) may be performed in a solvent. Thesolvent is preferably water or an organic solvent, and examples thereofinclude water, alcohols, carboxylic acids, ethers, halogenatedhydrocarbons, and aromatic hydrocarbons.

Examples of the alcohol include methanol, ethanol, 1-propanol, andisopropanol. Of these, methanol and ethanol are preferred.

Examples of the carboxylic acids include acetic acid and propionic acid.Of these, acetic acid is preferred.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane,and diethylene glycol diethyl ether, of which diethyl ether andtetrahydrofuran are preferred.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, ofwhich dichloromethane and chloroform are preferred.

Examples of the aromatic hydrocarbon include benzene, toluene, andxylene, of which benzene and toluene are preferred.

The ozonolysis temperature in the step (201) is preferably −78 to 200°C., and more preferably 0 to 150° C.

The ozonolysis pressure in the step (201) is preferably 0 to 5.0 MPa,and more preferably 0.1 to 1.0 MPa.

The ozonolysis duration in the step (201) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

The compound (70) may also be produced by a production method including:

a step (301) of epoxidizing a compound (300) represented by the formula:

(wherein R¹⁰ and Y are defined as described above; and R¹⁰⁰ is an alkylgroup) to provide a compound (301) represented by the formula:

(wherein R¹⁰, R¹⁰⁰, and Y are defined as described above);

a step (302) of reacting the compound (301) and lithium dialkylcopperrepresented by R¹⁰² ₂CuLi (wherein R¹⁰² is an alkyl group) to provide acompound (302) represented by the formula:

(wherein R¹⁰, R¹⁰⁰, R¹⁰², and Y are defined as described above); and

a step (303) of oxidizing the compound (302) to provide the compound(70).

The alkyl groups for R¹⁰ and R¹⁰² constitute the aforementioned R¹¹ inthe form of R¹⁰⁰R¹⁰²—CH—.

The two R¹⁰⁰s are the same as or different from each other. The twoR¹⁰²s are the same as or different from each other.

The epoxidation in the step (301) may be performed by causing anepoxidizing agent to act on the compound (300).

Examples of the epoxidizing agent include peroxy acids such asmeta-chloroperbenzoic acid (m-CPBA), perbenzoic acid, hydrogen peroxide,and tert-butyl hydroperoxide, dimethyl dioxirane, and methyltrifluoromethyl dioxirane, of which peroxy acids are preferred, andmeta-chloroperbenzoic acid is more preferred.

The epoxidizing agent may be used in an amount of 0.5 to 10.0 mol basedon 1 mol of the compound (300).

The epoxidation in the step (301) may be performed in a solvent. Thesolvent is preferably an organic solvent, and examples thereof includeketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons,nitriles, pyridines, nitrogen-containing polar organic compounds, anddimethyl sulfoxide, of which dichloromethane is preferred.

Examples of the ketones include acetone, methyl ethyl ketone, methylisobutyl ketone, cyclohexanone, and diacetone alcohol, of which acetoneis preferred.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane,and diethylene glycol diethyl ether, of which diethyl ether andtetrahydrofuran are preferred.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, ofwhich dichloromethane and chloroform are preferred.

Examples of the aromatic hydrocarbon include benzene, toluene, andxylene, of which benzene and toluene are preferred.

Examples of the nitrile include acetonitrile, propionitrile,butyronitrile, isobutyronitrile, and benzonitrile, of which acetonitrileis preferred.

Examples of the nitrogen-containing polar organic compound includeN,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone,2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, of whichN,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidoneare preferred.

The epoxidation temperature in the step (301) is preferably −78 to 200°C., and more preferably −40 to 150° C.

The epoxidation pressure in the step (301) is preferably 0 to 5.0 MPa,and more preferably 0.1 to 1.0 MPa.

The epoxidation duration in the step (301) is preferably 0.1 to 72hours, and more preferably 0.1 to 48 hours.

In the step (302), the lithium dialkylcopper may be used in an amount of0.5 to 10.0 mol based on 1 mol of the compound (301).

The reaction in the step (302) may be performed in a solvent. Thesolvent is preferably an organic solvent, and examples thereof includeethers, halogenated hydrocarbons, and aromatic hydrocarbons.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane,and diethylene glycol diethyl ether, of which diethyl ether andtetrahydrofuran are preferred.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, ofwhich dichloromethane and chloroform are preferred.

Examples of the aromatic hydrocarbon include benzene, toluene, andxylene, of which benzene and toluene are preferred.

The reaction temperature in the step (302) is preferably −78 to 200° C.,and more preferably −40 to 150° C.

The reaction pressure in the step (302) is preferably 0 to 5.0 MPa, andmore preferably 0.1 to 1.0 MPa.

The reaction duration in the step (302) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

Examples of the method of oxidizing the compound (302) in the step (303)include (a) a method of using Jones reagent (CrO₃/H₂SO₄) (Jonesoxidation), (b) a method of using Dess-Martin periodinane (DMP)(Dess-Martin oxidation), (c) a method of using pyridinium chlorochromate(PCC), (d) a method of causing a bleaching agent (about 5 to 6% aqueoussolution of NaOCl) to act in the presence of a nickel compound such asNiCl₂, and (e) a method of causing a hydrogen acceptor such as analdehyde and a ketone to act in the presence of an aluminum catalystsuch as Al(CH₃)₃ or Al[OCH(CH₃)₂]₃ (Oppenauer oxidation).

The oxidation in the step (303) may be performed in a solvent. Thesolvent is preferably water or an organic solvent, and examples thereofinclude water, ketones, alcohols, ethers, halogenated hydrocarbons,aromatic hydrocarbons, and nitriles.

Examples of the ketones include acetone, methyl ethyl ketone, methylisobutyl ketone, cyclohexanone, and diacetone alcohol, of which acetoneis preferred.

Examples of the alcohol include methanol, ethanol, 1-propanol, andisopropanol. Of these, methanol and ethanol are preferred.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane,and diethylene glycol diethyl ether, of which diethyl ether andtetrahydrofuran are preferred.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, ofwhich dichloromethane and chloroform are preferred.

Examples of the aromatic hydrocarbon include benzene, toluene, andxylene, of which benzene and toluene are preferred.

Examples of the nitrile include acetonitrile, propionitrile,butyronitrile, isobutyronitrile, and benzonitrile, of which acetonitrileis preferred.

The oxidation temperature in the step (303) is preferably −78 to 200°C., and may appropriately be selected in accordance with the methodused.

The oxidation pressure in the step (303) is preferably 0 to 5.0 MPa, andmay appropriately be selected in accordance with the method used.

The oxidation duration in the step (303) is preferably 0.1 to 72 hours,and may appropriately be selected in accordance with the method used.

The compound (70) may also be produced by a production method includinga step (401) of oxidizing a compound (400) represented by the formula:

(wherein R¹⁰ and Y are defined as described above; and R¹⁰⁰ is an alkylgroup) to provide the compound (70).

The oxidation in the step (401) may be performed by causing an oxidizingagent to act on the compound (400) in the presence of water and apalladium compound.

Examples of the oxidizing agent include monovalent or divalent coppersalts such as copper chloride, copper acetate, copper cyanide, andcopper trifluoromethanethiolate, iron salts such as iron chloride, ironacetate, iron cyanide, iron trifluoromethanethiolate, andhexacyanoferrates, benzoquinones such as 1,4-benzoquinone,2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetrachloro-1,2-benzoquinone,and tetrachloro-1,4-benzoquinone, H₂O₂, MnO₂, KMnO₄, RuO₄,m-chloroperbenzoic acid, and oxygen, and any combination of these. Ofwhich, copper salts, iron salts, and benzoquinones are preferred, andcopper chloride, iron chloride, and 1,4-benzoquinone are more preferred.

The oxidizing agent may be used in an amount of 0.001 to 10 mol based on1 mol of the compound (400).

The water may be used in an amount of 0.5 to 1,000 mol based on 1 mol ofthe compound (400).

An example of the palladium compound is palladium dichloride. Thepalladium compound may be used in a catalytic amount, and may be used inan amount of 0.0001 to 1.0 mol based on 1 mol of the compound (400).

The oxidation in the step (401) may be performed in a solvent. Examplesof the solvent include water, esters, aliphatic hydrocarbons, aromatichydrocarbons, alcohols, carboxylic acids, ethers, halogenatedhydrocarbons, nitrogen-containing polar organic compounds, nitriles,dimethyl sulfoxide, and sulfolane.

Examples of the esters include ethyl acetate, butyl acetate, ethyleneglycol monomethyl ether acetate, and propylene glycol monomethyl etheracetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), of whichethyl acetate is preferred.

Examples of the aliphatic hydrocarbons include hexane, cyclohexane,heptane, octane, nonane, decane, undecane, dodecane, and mineralspirits, of which cyclohexane and heptane are preferred.

Examples of the aromatic hydrocarbon include benzene, toluene, andxylene, of which benzene and toluene are preferred.

Examples of the alcohol include methanol, ethanol, 1-propanol, andisopropanol.

Examples of the carboxylic acids include acetic acid and propionic acid.Of these, acetic acid is preferred.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane,and diethylene glycol diethyl ether, of which diethyl ether andtetrahydrofuran are preferred.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, ofwhich dichloromethane and chloroform are preferred.

Examples of the nitrogen-containing polar organic compound includeN,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone,2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, of whichN,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidoneare preferred.

Examples of the nitrile include acetonitrile, propionitrile,butyronitrile, isobutyronitrile, and benzonitrile, of which acetonitrileis preferred.

The oxidation temperature in the step (401) is preferably −78 to 200°C., and more preferably −20 to 150° C.

The oxidation pressure in the step (401) is preferably 0 to 10 MPa, andmore preferably 0.1 to 5.0 MPa.

The oxidation duration in the step (401) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

The compound (100), the compound (300), and the compound (400) each maybe produced by a production method including a step (501) of causing areducing agent to act on an aldehyde represented by the formula:

wherein R¹⁰ and Y are defined as described above; and R¹⁰⁰ is an alkylgroup) to provide the compound (100).

In the step (501), the aldehyde is dimerized by reductive couplingreaction to generate the compound (100), the compound (300), or thecompound (400). Examples of the reducing agent used in the step (501)include samarium diiodide, titanium dichloride, vanadium trichloride,titanium tetrachloride, bis(cyclooctadiene)nickel, copper, magnesium,zinc, sodium, cerium trichloride, chromium oxide, and triphenyltinhydride. The reducing agents may be used in combination. The amount ofthe reducing agent used is preferably 0.001 to 10 mol, more preferably0.01 to 5 mol, and still more preferably 0.1 to 2 mol, based on 1 mol ofthe aldehyde.

The reaction in the step (501) may be performed in a solvent. Thesolvent is preferably an organic solvent, more preferably an ether, ahalogenated hydrocarbon, a pyridine, a nitrile, an aromatic hydrocarbon,or the like.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane,and diethylene glycol diethyl ether, of which diethyl ether andtetrahydrofuran are preferred.

Examples of the halogenated hydrocarbon include dichloromethane,dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, ofwhich dichloromethane and chloroform are preferred.

Examples of the nitrile include acetonitrile, propionitrile,butyronitrile, isobutyronitrile, and benzonitrile, of which acetonitrileis preferred.

Examples of the aromatic hydrocarbon include benzene, toluene, andxylene, of which benzene and toluene are preferred.

The reaction in step (501) is preferably performed in the presence of analcohol. Examples of the alcohol include methanol, ethanol, andisopropanol.

The reaction temperature in the step (501) is preferably −78 to 200° C.,and more preferably −20 to 100° C.

The reaction pressure in the step (501) is preferably 0 to 5.0 MPa, andmore preferably 0.1 to 1.0 MPa.

The reaction duration in the step (501) is preferably 0.1 to 72 hours,and more preferably 0.1 to 48 hours.

In any of the production methods described above, after the completionof each step, the solvent may be distilled off, or distillation,purification or the like may be performed to increase the purity of theresulting compounds. For the resulting compounds in which M is H, suchas those containing —COOH, —SO₃H, or —OSO₃H, the compounds may bebrought into contact with an alkali such as sodium carbonate or ammoniato covert these groups into the form of a salt.

The compound (12), the compound (21), the compound (32), the compound(41), the compound (51), the compound (62), and the compound (71) arenovel compounds.

The surfactant may be in the form of an aqueous solution containingwater and a surfactant (1) represented by the following general formula(1):

wherein R¹ to R⁵ each represent H or a monovalent substituent, with theproviso that at least one of R¹ and R³ represents a group represented bythe general formula: —Y—R⁶ and at least one of R² and R⁵ represents agroup represented by the general formula: —X-A or a group represented bythe general formula: —Y—R⁶;

X is the same or different at each occurrence and represents a divalentlinking group or a direct bond;

A is the same or different at each occurrence and represents —COOM,—SO₃M, or —OSO₃M, wherein M is H, a metal atom, NR⁷ ₄, imidazoliumoptionally having a substituent, pyridinium optionally having asubstituent, or phosphonium optionally having a substituent, wherein R⁷is H or an organic group;

Y is the same or different at each occurrence and represents a divalentlinking group selected from the group consisting of —S(═O)₂—, —O—,—COO—, —OCO—, —CONR⁸—, and —NR⁸CO—, or a direct bond, wherein R⁸ is H oran organic group;

R⁶ is the same or different at each occurrence and represents an alkylgroup having 2 or more carbon atoms and optionally containing, betweencarbon atoms, at least one selected from the group consisting of acarbonyl group, an ester group, an amide group, and a sulfonyl group;and

any two of R¹ to R⁵ optionally bind to each other to form a ring.

The upper limit of the concentration of the surfactant (1) in theaqueous solution is preferably 50% by mass, more preferably 30% by mass,still more preferably 20% by mass, further preferably 100,000 ppm, stillmore preferably 50,000 ppm, particularly preferably 10,000 ppm, and mostpreferably 5,000 ppm. The lower limit thereof is preferably 1 ppm, morepreferably 10 ppm, and still more preferably 50 ppm.

The surfactant is preferably a surfactant for polymerization used forproducing a fluoropolymer or an aqueous solution of a surfactant forpolymerization used for producing a fluoropolymer.

The method for producing a fluoropolymer of the present inventionincludes polymerizing a fluoromonomer in an aqueous medium to provide afluoropolymer. The polymerization may be emulsion polymerization, forexample.

The fluoromonomer preferably has at least one double bond.

The fluoromonomer is preferably at least one selected from the groupconsisting of tetrafluoroethylene (TFE), hexafluoropropylene (HFP),chlorotrifluoroethylene (CTFE), vinyl fluoride, vinylidene fluoride(VDF), trifluoroethylene, fluoroalkyl vinyl ether, fluoroalkyl ethylene,trifluoropropylene, pentafluoropropylene, trifluorobutene,tetrafluoroisobutene, hexafluoroisobutene, a fluoromonomer representedby the general formula (100): CH₂═CFRf¹⁰¹ (wherein Rf¹⁰¹ is a linear orbranched fluoroalkyl group having 1 to 12 carbon atoms), a fluorinatedvinyl heterocyclic compound, and a monomer that provides a crosslinkingsite.

The fluoroalkyl vinyl ether is preferably, for example, at least oneselected from the group consisting of:

a fluoromonomer represented by the general formula (110):CF₂═CF—ORf¹¹¹

wherein Rf¹¹¹ represents a perfluoroorganic group;

a fluoromonomer represented by the general formula (120):CF₂═CF—OCH₂—Rf¹²¹

wherein Rf¹²¹ represents a perfluoroalkyl group having 1 to 5 carbonatoms;

a fluoromonomer represented by the general formula (130):CF₂═CFOCF₂ORf¹³¹

wherein Rf¹³¹ is a linear or branched perfluoroalkyl group having 1 to 6carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms,or a linear or branched perfluorooxyalkyl group having 2 to 6 carbonatoms and containing 1 to 3 oxygen atoms;

a fluoromonomer represented by the general formula (140):CF₂═CFO(CF₂CF(Y¹⁴¹)O)_(m)(CF₂)_(n)F

wherein Y¹⁴¹ represents a fluorine atom or a trifluoromethyl group; m isan integer of 1 to 4; and n is an integer of 1 to 4; and

a fluoromonomer represented by the general formula (150):CF₂═CF—O—(CF₂CFY¹⁵¹—O)_(n)—(CFY¹⁵²)_(m)-A¹⁵¹wherein Y¹⁵¹ represents a fluorine atom, a chlorine atom, a —SO₂F group,or a perfluoroalkyl group; the perfluoroalkyl group optionally containsether oxygen and a —SO₂F group; n represents an integer of 0 to 3; nY¹⁵¹s are the same as or different from each other; Y¹⁵² represents afluorine atom, a chlorine atom, or a —SO₂F group; m represents aninteger of 1 to 5; m Y¹⁵²s are the same as or different from each other;A¹⁵¹ represents —SO₂X¹⁵¹, —COZ¹⁵¹, or —POZ¹⁵²Z¹⁵³; X¹⁵¹ represents F,Cl, Br, I, —OR¹⁵¹, or —NR¹⁵²R¹⁵³; Z¹⁵¹, Z¹⁵², and Z¹⁵³ are the same asor different from each other, and each represent —NR¹⁵⁴R¹⁵⁵ or —OR¹⁵⁶;R¹⁵¹, R¹⁵², R¹⁵³, R¹⁵⁴, R¹⁵⁵, and R¹⁵⁶ are the same as or different fromeach other, and each represent H, ammonium, an alkali metal, or an alkylgroup, aryl group, or sulfonyl-containing group optionally containing afluorine atom.

The “perfluoroorganic group” as used herein means an organic group inwhich all hydrogen atoms bonded to the carbon atoms are replaced byfluorine atoms. The perfluoroorganic group optionally has ether oxygen.

An example of the fluoromonomer represented by the general formula (110)is a fluoromonomer in which Rf¹¹¹ is a perfluoroalkyl group having 1 to10 carbon atoms. The perfluoroalkyl group preferably has 1 to 5 carbonatoms.

Examples of the perfluoroorganic group in the general formula (110)include a perfluoromethyl group, a perfluoroethyl group, aperfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group,and a perfluorohexyl group.

Examples of the fluoromonomer represented by the general formula (110)also include those represented by the general formula (110) in whichRf¹¹¹ is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms;those in which Rf¹¹¹ is a group represented by the following formula:

wherein m represents 0 or an integer of 1 to 4; and those in which Rf¹¹¹is a group represented by the following formula:

wherein n represents an integer of 1 to 4.

Of these, the fluoromonomer represented by the general formula (110) ispreferably

a fluoromonomer represented by the general formula (160):CF₂═CF—ORf¹⁶¹wherein Rf¹⁶¹ represents a perfluoroalkyl group having 1 to 10 carbonatoms. Rf¹⁶¹ is preferably a perfluoroalkyl group having 1 to 5 carbonatoms.

The fluoroalkyl vinyl ether is preferably at least one selected from thegroup consisting of fluoromonomers represented by the general formulas(160), (130), and (140).

The fluoromonomer represented by the general formula (160) is preferablyat least one selected from the group consisting of perfluoro(methylvinyl ether), perfluoro(ethyl vinyl ether), and perfluoro(propyl vinylether), and is more preferably at least one selected from the groupconsisting of perfluoro(methyl vinyl ether) and perfluoro(propyl vinylether).

The fluoromonomer represented by the general formula (130) is preferablyat least one selected from the group consisting of CF₂═CFOCF₂OCF₃,CF₂═CFOCF₂OCF₂CF₃, and CF₂═CFOCF₂OCF₂CF₂OCF₃.

The fluoromonomer represented by the general formula (140) is preferablyat least one selected from the group consisting ofCF₂═CFOCF₂CF(CF₃)O(CF₂)₃F, CF₂═CFO(CF₂CF(CF₃)O)₂(CF₂)₃F, andCF₂═CFO(CF₂CF(CF₃)O)₂ (CF₂)₂F.

The fluoromonomer represented by the general formula (150) is preferablyat least one selected from the group consisting of CF₂═CFOCF₂CF₂SO₂F,CF₂═CFOCF₂CF(CF₃)OCF₂CF₂SO₂F, CF₂═CFOCF₂CF(CF₂CF₂SO₂F)OCF₂CF₂SO₂F, andCF₂═CFOCF₂CF(SO₂F)₂.

The fluoromonomer represented by the general formula (100) is preferablya fluoromonomer in which Rf¹⁰¹ is a linear fluoroalkyl group, and morepreferably a fluoromonomer in which Rf¹⁰¹ is a linear perfluoroalkylgroup. Rf¹⁰¹ preferably has 1 to 6 carbon atoms. Examples of thefluoromonomer represented by the general formula (100) includeCH₂═CFCF₃, CH₂═CFCF₂CF₃, CH₂═CFCF₂CF₂CF₃, CH₂═CFCF₂CF₂CF₂H, andCH₂═CFCF₂CF₂CF₂CF₃, of which preferred is 2,3,3,3-tetrafluoropropylenerepresented by CH₂═CFCF₃.

The fluoroalkyl ethylene is preferably a fluoroalkyl ethylenerepresented by the general formula (170):CH₂═CH—(CF₂)_(n)—X¹⁷¹

(wherein X¹⁷¹ is H or F; and n is an integer of 3 to 10), and morepreferably at least one selected from the group consisting ofCH₂═CH—C₄F₉ and CH₂═CH—C₆F₁₃.

An example of the fluorinated vinyl heterocyclic compound is afluorinated vinyl heterocyclic compound represented by the generalformula (230):

wherein X²³¹ and X²³² are each independently F, Cl, a methoxy group, ora fluorinated methoxy group; and Y²³¹ is represented by the formula Y²³²or Y²³³:

wherein Z²³¹ and Z²³² are each independently F or a fluorinated alkylgroup having 1 to 3 carbon atoms.

The monomer that provides a crosslinking site is preferably at least oneselected from the group consisting of:

-   -   a fluoromonomer represented by the general formula (180):        CX¹⁸¹ ₂═CX¹⁸²—R_(f) ¹⁸¹CHR¹⁸¹X¹⁸³

wherein X¹⁸¹ and X¹⁸² are each independently a hydrogen atom, a fluorineatom, or CH₃; R_(f) ¹⁸¹ is a fluoroalkylene group, a perfluoroalkylenegroup, a fluoro(poly)oxyalkylene group, or a perfluoro(poly)oxyalkylenegroup; R¹⁸¹ is a hydrogen atom or CH₃; and X¹⁸³ is an iodine atom or abromine atom;

a fluoromonomer represented by the general formula (190):CX¹⁹¹ ₂═CX¹⁹²—R_(f) ¹⁹¹X¹⁹³

wherein X¹⁹¹ and X¹⁹² are each independently a hydrogen atom, a fluorineatom, or CH₃; R_(f) ¹⁹¹ is a fluoroalkylene group, a perfluoroalkylenegroup, a fluoropolyoxyalkylene group, or a perfluoropolyoxyalkylenegroup; and X¹⁹³ is an iodine atom or a bromine atom;

a fluoromonomer represented by the general formula (200):CF₂═CFO(CF₂CF(CF₃)O)_(m)(CF₂)_(n)—X²⁰¹

wherein m is an integer of 0 to 5; n is an integer of 1 to 3; and X²⁰¹is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodineatom, a bromine atom, or —CH₂I; and

a fluoromonomer represented by the general formula (210):CH₂═CFCF₂O(CF(CF₃)CF₂O)_(m)(CF(CF₃))_(n)—X²⁰¹wherein m is an integer of 0 to 5; n is an integer of 1 to 3; and X²¹¹is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodineatom, a bromine atom, or —CH₂OH; and

a monomer represented by the general formula (220):CR²²¹R²²²═CR²²³Z²²¹—CR²²⁴═CR²²⁵R²²⁶

wherein R²²¹, R²²², R²²³, R²²⁴, R²²⁵, and R²²⁶ are the same as ordifferent from each other, and are each a hydrogen atom or an alkylgroup having 1 to 5 carbon atoms; Z²²¹ is a linear or branched alkylenegroup having 1 to 18 carbon atoms and optionally having an oxygen atom,a cycloalkylene group having 3 to 18 carbon atoms, an at least partiallyfluorinated alkylene or oxyalkylene group having 1 to 10 carbon atoms,or a (per)fluoropolyoxyalkylene group which is represented by:-(Q)_(p)-CF₂O—(CF₂CF₂O)_(m)(CF₂O)_(n)—CF₂-(Q)_(p)-

(wherein Q is an alkylene group or an oxyalkylene group; p is 0 or 1;and m/n is 0.2 to 5) and has a molecular weight of 500 to 10,000.

X¹⁸³ and X¹⁹³ are each preferably an iodine atom. R_(f) ¹⁸¹ and R_(f)¹⁹¹ are each preferably a perfluoroalkylene group having 1 to 5 carbonatoms. R¹⁸¹ is preferably a hydrogen atom. X²⁰¹ is preferably a cyanogroup, an alkoxycarbonyl group, an iodine atom, a bromine atom, or—CH₂I. X²¹¹ is preferably a cyano group, an alkoxycarbonyl group, aniodine atom, a bromine atom, or —CH₂OH.

The monomer that provides a crosslinking site is preferably at least oneselected from the group consisting of CF₂═CFOCF₂CF(CF₃)OCF₂CF₂CN,CF₂═CFOCF₂CF(CF₃)OCF₂CF₂COOH, CF₂═CFOCF₂CF(CF₃)OCF₂CF₂CH₂I,CF₂═CFOCF₂CF₂CH₂I, CH₂═CFCF₂OCF(CF₃)CF₂OCF(CF₃)CN,CH₂═CFCF₂OCF(CF₃)CF₂OCF(CF₃)COOH, CH₂═CFCF₂OCF(CF₃)CF₂OCF(CF₃)CH₂OH,CH₂═CHCF₂CF₂I, CH₂═CH(CF₂)₂CH═CH₂, CH₂═CH(CF₂)₆CH═CH₂, andCF₂═CFO(CF₂)₅CN, and is more preferably at least one selected from thegroup consisting of CF₂═CFOCF₂CF(CF₃)OCF₂CF₂CN and CF₂═CFOCF₂CF₂CH₂I.

In the above step, the fluoromonomer may be polymerized with afluorine-free monomer. An example of the fluorine-free monomer is ahydrocarbon monomer reactive with the fluoromonomer. Examples of thehydrocarbon monomer include alkenes such as ethylene, propylene,butylene, and isobutylene; alkyl vinyl ethers such as ethyl vinyl ether,propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, andcyclohexyl vinyl ether; vinyl esters such as vinyl acetate, vinylpropionate, vinyl n-butyrate, vinyl isobutyrate, vinyl valerate, vinylpivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinylversatate, vinyl laurate, vinyl myristate, vinyl palmitate, vinylstearate, vinyl benzoate, vinyl para-t-butylbenzoate, vinylcyclohexanecarboxylate, monochlorovinyl acetate, vinyl adipate, vinylacrylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinylcinnamate, vinyl undecylenate, vinyl hydroxyacetate, vinylhydroxypropionate, vinyl hydroxybutyrate, vinyl hydroxyvalerate, vinylhydroxyisobutyrate, and vinyl hydroxycyclohexanecarboxylate; alkyl allylethers such as ethyl allyl ether, propyl allyl ether, butyl allyl ether,isobutyl allyl ether, and cyclohexyl allyl ether; and alkyl allyl esterssuch as ethyl allyl ester, propyl allyl ester, butyl allyl ester,isobutyl allyl ester, and cyclohexyl allyl ester.

The fluorine-free monomer may also be a functional group-containinghydrocarbon monomer (other than monomers that provide a crosslinkingsite). Examples of the functional group-containing hydrocarbon monomerinclude hydroxy alkyl vinyl ethers such as hydroxyethyl vinyl ether,hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutylvinyl ether, and hydroxycyclohexyl vinyl ether; fluorine-free monomershaving carboxyl groups such as itaconic acid, succinic acid, succinicanhydride, fumaric acid, fumaric anhydride, crotonic acid, maleic acid,maleic anhydride, and perfluorobutenoic acid; fluorine-free monomershaving a glycidyl group such as glycidyl vinyl ether and glycidyl allylether; fluorine-free monomers having an amino group such as aminoalkylvinyl ether and aminoalkyl allyl ether; and fluorine-free monomershaving an amide group such as (meth)acrylamide and methylol acrylamide.

In the above step, desired fluoropolymer particles can be obtained bypolymerizing one or two or more of the above fluoromonomers.

In the production method of the present invention, the presence of atleast one of the above surfactants can efficiently provide afluoropolymer. In the production method of the present invention, two ormore of the surfactants may be used as the surfactant in combination,and a compound having a surfactant function other than the surfactantsmay be used in combination insofar as the compound is volatile or isallowed to remain in a molded body formed from the fluoropolymer or thelike.

In the production method of the present invention, the polymerization isalso preferably performed in the presence of a nonionic surfactant. Thenonionic surfactant is preferably at least one selected from the groupconsisting of:

a compound represented by the general formula (240):Rf²⁴¹—(X²⁴¹)_(n)—Y²⁴¹

wherein Rf²⁴¹ is a partially fluorinated alkyl group or a fullyfluorinated alkyl group having 1 to 12 carbon atoms; n is 0 or 1; X²⁴¹is —O—, —COO—, or —OCO—; Y²⁴ is —(CH₂)_(p)H, —(CH₂)_(p)OH, or—(OR²⁴¹)_(q) (OR²⁴²)_(r)OH; p is an integer of 1 to 12; q is an integerof 1 to 12; r is an integer of 0 to 12; and R²⁴1 and R²⁴² are each analkylene group having 2 to 4 carbon atoms, with the proviso that R²⁴1and R²⁴² are different from each other;

a block polymer represented by the general formula (250):H(OR²⁵¹)_(u)(OR²⁵²)_(v)OHherein R²⁵ and R²⁵² are each an alkylene group having 1 to 4 carbonatoms; u and v are each an integer of 1 to 5, with the proviso that R²⁵and R²⁵² are different from each other;

a nonionic polymer having a hydrophobic group containing a hydrocarbongroup having 8 to 20 carbon atoms and a hydrophilic group containing apolyalkylene oxide in the molecule; and

a silicon compound represented by the general formula (260):R²⁶¹ _(m)—Si—(OR²⁶²)_(4-m)

wherein R²⁶¹ is an alkyl group having 1 to 12 carbon atoms; R²⁶² is analkyl group having 1 to 4 carbon atoms; and m is an integer of 1 to 3.

Specific examples of the block polymer represented by the generalformula (250) include block polymers composed of at least two segmentsselected from the group consisting of polyoxyethylene, polyoxypropylene,and polyoxybutylene. Examples thereof includepolyoxyethylene-polyoxypropylene block polymers andpolyoxyethylene-polyoxybutylene block polymers, and not only A-B blockpolymers but also A-B-A block polymers are preferred. More preferably,use of a polyoxyethylene-polyoxypropylene block polymer or apolyoxypropylene-polyoxyethylene-polyoxypropylene block polymer allowsto prepare a stable fluoropolymer dispersion at a high concentration. Inaddition, the content of the polyoxyethylene segment is preferably 10 to50% in view of reducing generation of agglomerates considered to becaused by re-agglomeration, and more preferably 20 to 40% because itallows for the preparation of low viscosity fluoropolymer dispersions.The polyoxyethylene segment may have a molecular weight of, but notlimited to, 1,000 to 7,000 g/mol, and in particular, the use of apolyoxyethylene segment having a molecular weight of 2,500 to 6,500g/mol allows to prepare a dispersion having a low viscosity andexcellent dispersibility.

In the production method of the present invention, a nucleating agentmay be used. The nucleating agent is preferably used in an amountappropriately selected in accordance with the type of the nucleatingagent. For example, the amount thereof is 1,000 ppm or less, morepreferably 500 ppm or less, still more preferably 100 ppm or less,particularly preferably 50 ppm or less, and still further preferably 10ppm or less, based on the aqueous medium.

The use of the above nucleating agent allows for obtaining afluoropolymer having a smaller primary particle size than that in thecase of polymerization in the absence of the above nucleating agent.

Examples of the nucleating agent include dicarboxylic acids,perfluoropolyether (PFPE) acids or salts thereof, andhydrocarbon-containing surfactants other than the surfactant (1). Thenucleating agent is preferably free from an aromatic ring, and ispreferably an aliphatic compound.

Although the nucleating agent is preferably added before addition of thepolymerization initiator or simultaneously with addition of thepolymerization initiator, it is also possible to adjust the particlesize distribution by adding the nucleating agent during thepolymerization.

The amount of the dicarboxylic acid is preferably 1,000 ppm or less,more preferably 500 ppm or less, and still more preferably 100 ppm orless, based on the aqueous medium.

The perfluoropolyether (PFPE) acids or salts thereof may have any chainstructure in which the oxygen atoms in the main chain of the moleculeare separated by saturated carbon fluoride groups having 1 to 3 carbonatoms. Two or more carbon fluoride groups may be present in themolecule. Representative structures thereof have the repeating unitsrepresented by the following formulas:(—CFCF₃—CF₂—O—)_(n)  (VII)(—CF₂—CF₂—CF₂—O—)_(n)  (VIII)(—CF₂—CF₂—O—)_(n)—(—CF₂—O—)_(m)  (IX)(—CF₂—CFCF₃—O—)_(n)—(—CF₂—O—)_(m)  (X)

These structures are described in Kasai, J. Appl. Polymer Sci., 57,797(1995). As disclosed in this document, the PFPE acid or a saltthereof may have a carboxylic acid group or a salt thereof at one end orboth ends. The PFPE acid or a salt thereof may also have a sulfonicacid, a phosphonic acid group, or a salt thereof at one end or bothends. The PFPE acid or a salt thereof may have different groups at eachend. Regarding monofunctional PFPE, the other end of the molecule isusually perfluorinated, but may contain a hydrogen or chlorine atom. ThePFPE acid or a salt thereof has at least two ether oxygen atoms,preferably at least four ether oxygen atoms, and still more preferablyat least six ether oxygen atoms. Preferably, at least one carbonfluoride group separating ether oxygen atoms, more preferably at leasttwo of such carbon fluoride groups, have 2 or 3 carbon atoms. Still morepreferably, at least 50% of the carbon fluoride groups separating etheroxygen atoms has 2 or 3 carbon atoms. Also preferably, the PFPE acid ora salt thereof has at least 15 carbon atoms in total, and for example, apreferable minimum value of n or n+m in the repeating unit structure ispreferably at least 5. Two or more of the PFPE acids and salts thereofhaving an acid group at one end or both ends may be used in theproduction method of the present invention. The PFPE acid or a saltthereof preferably has a number average molecular weight of less than6,000 g/mol.

The hydrocarbon-containing surfactant is preferably added in an amountof 40 ppm or less, more preferably 30 ppm or less, and still morepreferably 20 ppm or less, based on the aqueous medium. The amounts inppm of the oleophilic nucleation sites present in the aqueous mediumwill be less than the amounts in ppm disclosed herein as being added tothe aqueous medium.

Thus, the amounts of oleophilic nucleation sites will each be less thanthe 50 ppm, 40 ppm, 30 ppm, and 20 ppm as mentioned above. Since it isconsidered that oleophilic nucleation sites exist as molecules, only asmall amount of the hydrocarbon-containing surfactant can generate alarge amount of oleophilic nucleation sites. Thus, addition of as littleas 1 ppm of the hydrocarbon-containing surfactant to the aqueous mediumcan provide beneficial effect. The lower limit value thereof ispreferably 0.01 ppm, and more preferably 0.1 ppm.

The hydrocarbon-containing surfactant encompasses nonionic surfactantsand cationic surfactants, including siloxane surfactants such as thosedisclosed in U.S. Pat. No. 7,897,682 (Brothers et al.) and U.S. Pat. No.7,977,438 (Brothers et al.).

The hydrocarbon-containing surfactant is preferably a nonionichydrocarbon surfactant. In other words, the nucleating surfactant ispreferably a nonionic hydrocarbon surfactant. The nonionic hydrocarbonsurfactant is preferably free from an aromatic moiety.

Examples of the nonionic surfactant include a compound represented bythe following general formula (i):R³—O-A₁-H  (i)

wherein R³ is a linear or branched primary or secondary alkyl grouphaving 8 to 18 carbon atoms, and Al is a polyoxyalkylene chain.

R³ preferably has 10 to 16, more preferably 12 to 16 carbon atoms. WhenR³ has 18 or less carbon atoms, the aqueous dispersion tends to havegood dispersion stability. Further, when R³ has more than 18 carbonatoms, it is difficult to handle due to its high flowing temperature.When R³ has less than 8 carbon atoms, the surface tension of the aqueousdispersion becomes high, so that the permeability and wettability arelikely to decrease.

The polyoxyalkylene chain may be composed of oxyethylene andoxypropylene. The polyoxyalkylene chain is composed of an averagerepeating number of 5 to 20 oxyethylene groups and an average repeatingnumber of 0 to 2 oxypropylene groups, and is a hydrophilic group. Thenumber of oxyethylene units may have either a broad or narrow monomodaldistribution as typically supplied, or a broader or bimodal distributionwhich may be obtained by blending. When the average number of repeatingoxypropylene groups is more than 0, the oxyethylene groups andoxypropylene groups in the polyoxyalkylene chain may be arranged inblocks or randomly.

From the viewpoint of viscosity and stability of the aqueous dispersion,a polyoxyalkylene chain composed of an average repeating number of 7 to12 oxyethylene groups and an average repeating number of 0 to 2oxypropylene groups is preferred. In particular, when Al has 0.5 to 1.5oxypropylene groups on average, low foaming properties are good, whichis preferable.

More preferably, R³ is (R′) (R″)HC—, where R′ and R″ are the same ordifferent linear, branched, or cyclic alkyl groups, and the total amountof carbon atoms is at least 5, preferably 7 to 17. Preferably, at leastone of R′ and R″ is a branched or cyclic hydrocarbon group.

Specific examples of the polyoxyethylene alkyl ether includeC₁₃H₂₇—O—(C₂H₄O)₁₀—H, C₁₂H₂₅—O—(C₂H₄O)₁₀—H,C₁₀H₂₁CH(CH₃)CH₂—O—(C₂H₄O)₉—H, C₁₃H₂₇—O—(C₂H₄O)₉—(CH(CH₃)CH₂O)—H,C₁₆H₃₃—O—(C₂H₄O)₁₀—H, and HC(C₅H₁₁)(C₇H₁₅)—O—(C₂H₄O)₉—H.

Examples of commercially available products of the polyoxyethylene alkylethers include Genapol X080 (product name, manufactured by Clariant),NOIGEN TDS series (manufactured by DKS Co., Ltd.) exemplified by NOIGENTDS-80 (trade name), LEOCOL TD series (manufactured by Lion Corp.)exemplified by LEOCOL TD-90 (trade name), LIONOL® TD series(manufactured by Lion Corp.), T-Det A series (manufactured by HarcrosChemicals Inc.) exemplified by T-Det A 138 (trade name), and TERGITOL®15 S series (manufactured by Dow).

The nonionic surfactant is preferably an ethoxylate of2,6,8-trimethyl-4-nonanol having about 4 to about 18 ethylene oxideunits on average, an ethoxylate of 2,6,8-trimethyl-4-nonanol havingabout 6 to about 12 ethylene oxide units on average, or a mixturethereof.

This type of nonionic surfactant is also commercially available, forexample, as TERGITOL TMN-6, TERGITOL TMN-10, and TERGITOL TMN-100X (allproduct names, manufactured by Dow Chemical Co., Ltd.).

The hydrophobic group of the nonionic surfactant may be any of analkylphenol group, a linear alkyl group, and a branched alkyl group.

Examples of the polyoxyethylene alkylphenyl ether-based nonioniccompound include, for example, a compound represented by the followinggeneral formula (ii):R⁴—C₆H₄—O-A²-H  (ii)wherein R⁴ is a linear or branched primary or secondary alkyl grouphaving 4 to 12 carbon atoms, and A² is a polyoxyalkylene chain. Specificexamples of the polyoxyethylene alkylphenyl ether-based nonioniccompound include Triton X-100 (trade name, manufactured by Dow ChemicalCo., Ltd.).

Examples of the nonionic surfactant also include polyol compounds.Specific examples thereof include those described in InternationalPublication No.

WO2011/014715.

Typical examples of the polyol compound include compounds having one ormore sugar units as a polyol unit.

The sugar units may have been modified to contain at least one longchain. Examples of suitable polyol compounds containing at least onelong chain moiety include alkyl glycosides, modified alkyl glycosides,sugar esters, and combinations thereof. Examples of the sugars include,but are not limited to, monosaccharides, oligosaccharides, andsorbitanes. Examples of monosaccharides include pentoses and hexoses.Typical examples of monosaccharides include ribose, glucose, galactose,mannose, fructose, arabinose, and xylose.

Examples of oligosaccharides include oligomers of 2 to 10 of the same ordifferent monosaccharides. Examples of oligosaccharides include, but arenot limited to, saccharose, maltose, lactose, raffinose, and isomaltose.

Typically, sugars suitable for use as the polyol compound include cycliccompounds containing a 5-membered ring of four carbon atoms and oneheteroatom (typically oxygen or sulfur, preferably oxygen atom), orcyclic compounds containing a 6-membered ring of five carbon atoms andone heteroatom as described above, preferably, an oxygen atom. Thesefurther contain at least two or at least three hydroxy groups (—OHgroups) bonded to the carbon ring atoms. Typically, the sugars have beenmodified in that one or more of the hydrogen atoms of a hydroxy group(and/or hydroxyalkyl group) bonded to the carbon ring atoms has beensubstituted by the long chain residues such that an ether or ester bondis created between the long chain residue and the sugar moiety.

The sugar-based polyol may contain a single sugar unit or a plurality ofsugar units. The single sugar unit or the plurality of sugar units maybe modified with long chain moieties as described above. Specificexamples of sugar-based polyol compounds include glycosides, sugaresters, sorbitan esters, and mixtures and combinations thereof.

A preferred type of polyol compounds are alkyl or modified alkylglucosides. These type of surfactants contains at least one glucosemoiety. Examples of alkyl or modified alkyl glucosides include compoundsrepresented by:

wherein x represents 0, 1, 2, 3, 4, or 5 and R¹ and R² eachindependently represent H or a long chain unit containing at least 6carbon atoms, with the proviso that at least one of R¹ and R² is not H.Typical examples of R¹ and R² include aliphatic alcohol residues.Examples of the aliphatic alcohols include hexanol, heptanol, octanol,nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol,hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearylalcohol), eicosanoic acid, and combinations thereof.

It is understood that the above formula represents specific examples ofalkyl poly glucosides showing glucose in its pyranose form but othersugars or the same sugars but in different enantiomeric ordiastereomeric forms may also be used.

Alkyl glucosides are available, for example, by acid-catalyzed reactionsof glucose, starch, or n-butyl glucoside with aliphatic alcohols whichtypically yields a mixture of various alkyl glucosides (Alkylpolygylcoside, Rompp, Lexikon Chemie, Version 2.0, Stuttgart/New York,Georg Thieme Verlag, 1999). Examples of the aliphatic alcohols includehexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol(lauryl alcohol), tetradecanol, hexadecanol (cetyl alcohol),heptadecanol, octadecanol (stearyl alcohol), eicosanoic acid, andcombinations thereof. Alkyl glucosides are also commercially availableunder the trade name GLUCOPON or DISPONIL from Cognis GmbH, Dusseldorf,Germany.

Examples of other nonionic surfactants include bifunctional blockcopolymers supplied from BASF as Pluronic® R series, tridecyl alcoholalkoxylates supplied from BASF Corporation as Iconol® TDA series, andhydrocarbon-containing siloxane surfactants, preferably hydrocarbonsurfactants. In the sense that the hydrocarbyl groups are fullysubstituted with hydrogen atoms where they can be substituted by halogensuch as fluorine, these siloxane surfactants can also be regarded ashydrocarbon surfactants, i.e. the monovalent substituents on thehydrocarbyl groups are hydrogen.

Also, in the production method of the present invention, in addition tothe surfactant and other compounds having a surfactant function used asnecessary, an additive may also be used to stabilize the compounds.Examples of the additive include a buffer, a pH adjuster, a stabilizingaid, and a dispersion stabilizer.

The stabilizing aid is preferably paraffin wax, fluorine-containing oil,a fluorine-containing solvent, silicone oil, or the like. Thestabilizing aids may be used alone or in combination of two or more. Thestabilizing aid is more preferably paraffin wax. The paraffin wax may bein the form of liquid, semi-solid, or solid at room temperature, and ispreferably a saturated hydrocarbon having 12 or more carbon atoms. Theparaffin wax usually preferably has a melting point of 40 to 65° C., andmore preferably 50 to 65° C.

The amount of the stabilizing aid used is preferably 0.1 to 12% by mass,and more preferably 0.1 to 8% by mass, based on the mass of the aqueousmedium used. It is desirable that the stabilizing aid is sufficientlyhydrophobic so that the stabilizing aid is completely separated from thePTFE aqueous emulsion after emulsion polymerization of TFE, and does notserve as a contaminating component.

In the production method of the present invention, the polymerization isperformed by charging a polymerization reactor with an aqueous medium,the surfactant, monomers, and optionally other additives, stirring thecontents of the reactor, maintaining the reactor at a predeterminedpolymerization temperature, and adding a predetermined amount of apolymerization initiator to thereby initiate the polymerizationreaction. After the initiation of the polymerization reaction, thecomponents such as the monomers, the polymerization initiator, a chaintransfer agent, and the surfactant may additionally be added dependingon the purpose. The surfactant may be added after the polymerizationreaction is initiated.

The polymerization is usually performed at a polymerization temperatureof 5 to 120° C. and a polymerization pressure of 0.05 to 10 MPaG. Thepolymerization temperature and the polymerization pressure aredetermined as appropriate in accordance with the types of the monomersused, the molecular weight of the target fluoropolymer, and the reactionrate.

For example, the polymerization temperature is more preferably 30° C. orhigher, and still more preferably 50° C. or higher. Further, thepolymerization temperature is more preferably 120° C. or lower, andstill more preferably 100° C. or lower.

Further, the polymerization pressure is more preferably 0.3 MPaG orhigher, still more preferably 0.5 MPaG or higher, and more preferably5.0 MPaG or lower, still more preferably 3.0 MPaG or lower. Inparticular, from the viewpoint of improving the yield of fluoropolymer,the polymerization pressure is preferably 1.0 MPaG or more, morepreferably 1.2 MPa or more, still more preferably 1.5 MPa or more, andparticularly preferably 2.0 MPaG or more.

The total amount of the surfactant added is preferably 0.0001 to 10% bymass based on 100% by mass of the aqueous medium. The lower limitthereof is more preferably 0.001% by mass, while the upper limit thereofis more preferably 1% by mass. Less than 0.0001% by mass of thesurfactant may cause insufficient dispersibility. More than 10% by massof the surfactant may fail to give the effects corresponding to itsamount; on the contrary, such an amount of the surfactant may cause areduction in the polymerization rate or even stop the reaction. Theamount of the compound added is appropriately determined in accordancewith factors such as the types of the monomers used and the molecularweight of the target fluoropolymer.

It is also preferable that the method for producing a fluoropolymer ofthe present invention further includes a step of continuously adding thesurfactant (1). Adding the surfactant (1) continuously means, forexample, adding the surfactant (1) not all at once, but adding over timeand without interruption or adding in portions. The surfactant (1) maybe added as an aqueous solution containing the surfactant (1) and water.

In the method for producing a fluoropolymer of the present invention,the step of continuously adding the surfactant (1) is preferably a stepof starting to add the surfactant (1) to the aqueous medium when thesolid content of the fluoropolymer formed in the aqueous medium is 0.5%by mass or less. The surfactant (1) is more preferably started to beadded when the solid content is 0.3% by mass or less, still morepreferably started to be added when the solid content is 0.2% by mass orless, further preferably started to be added when the solid content is0.1% by mass or less, and particularly preferably started to be addedwhen the polymerization is initiated. The solid content is aconcentration based on the total amount of the aqueous medium and thefluoropolymer.

In the step of continuously adding the surfactant (1), the surfactant(1) is preferably added in an amount of 0.0001 to 10% by mass, based on100% by mass of the aqueous medium. The lower limit thereof ispreferably 0.001% by mass, more preferably 0.01% by mass, and still morepreferably 0.1% by mass. The upper limit thereof is preferably 10% bymass, more preferably 1.0% by mass, and still more preferably 0.50% bymass. Less than 0.0001% by mass of the surfactant may cause insufficientdispersibility. More than 10% by mass of the surfactant may fail to givethe effects corresponding to its amount; on the contrary, such an amountof the surfactant may cause a reduction in the polymerization rate oreven stop the reaction. The amount of the compound added isappropriately determined in accordance with factors such as the types ofthe monomers used and the molecular weight of the target fluoropolymer.

The step of obtaining the fluoropolymer is preferably a step ofpolymerizing the fluoromonomer substantially in the absence of afluorine-containing surfactant.

Conventionally, fluorine-containing surfactants have been used for thepolymerization of fluoropolymers, but the production method of thepresent invention allows for obtaining fluoropolymers without using thefluorine-containing surfactants by using the surfactant (1).

The expression “substantially in the absence of a fluorine-containingsurfactant” as used herein means that the amount of thefluorine-containing surfactant in the aqueous medium is 10 ppm or less,preferably 1 ppm or less, more preferably 100 ppb or less, still morepreferably 10 ppb or less, and further preferably 1 ppb or less.

Examples of the fluorine-containing surfactant include anionicfluorine-containing surfactants.

The anionic fluorine-containing surfactant may be, for example, afluorine atom-containing surfactant having 20 or less carbon atoms intotal in the portion excluding the anionic group.

The fluorine-containing surfactant may also be a surfactant containingfluorine having a molecular weight of 800 or less in the anionic moiety.

The “anionic moiety” means the portion of the fluorine-containingsurfactant excluding the cation. For example, in the case ofF(CF₂)_(n1)COOM represented by the formula (I) described later, theanionic moiety is the “F(CF₂)_(n1)COO” portion.

Examples of the fluorine-containing surfactant also includefluorine-containing surfactants having a Log POW of 3.5 or less. The LogPOW is a partition coefficient between 1-octanol and water, which isrepresented by Log P (wherein P represents the ratio between theconcentration of the fluorine-containing surfactant in octanol and theconcentration of the fluorine-containing surfactant in water in aphase-separated octanol/water (1:1) liquid mixture containing thefluorine-containing surfactant).

Log POW is determined as follows. Specifically, HPLC is performed onstandard substances (heptanoic acid, octanoic acid, nonanoic acid, anddecanoic acid) each having a known octanol/water partition coefficientusing TOSOH ODS-120T column (ϕ4.6 mm×250 mm, Tosoh Corp.) as a columnand acetonitrile/0.6% by mass HClO4 aqueous solution=1/1 (vol/vol %) asan eluent at a flow rate of 1.0 ml/min, a sample amount of 300 μL, and acolumn temperature of 40° C.; with a detection light of UV 210 nm. Foreach standard substance, a calibration curve is drawn with respect tothe elution time and the known octanol/water partition coefficient.Based on the calibration curve, Log POW is calculated from the elutiontime of the sample liquid in HPLC.

Specific examples of the fluorine-containing surfactant include thosedisclosed in U.S. Patent Application Publication No. 2007/0015864, U.S.Patent Application Publication No. 2007/0015865, U.S. Patent ApplicationPublication No. 2007/0015866, and U.S. Patent Application PublicationNo. 2007/0276103, U.S. Patent Application Publication No. 2007/0117914,U.S. Patent Application Publication No. 2007/142541, U.S. PatentApplication Publication No. 2008/0015319, U.S. Pat. Nos. 3,250,808,3,271,341, Japanese Patent Laid-Open No. 2003-119204, InternationalPublication No. WO2005/042593, International Publication No.WO2008/060461, International Publication No. WO2007/046377,International Publication No. WO2007/119526, International PublicationNo. WO2007/046482, International Publication No. WO2007/046345, U.S.Patent Application Publication No. 2014/0228531, InternationalPublication No. WO2013/189824, and International Publication No.WO2013/189826.

Examples of the anionic fluorine-containing surfactant include acompound represented by the following general formula (N⁰):X^(n0)—Rf^(n0)—Y⁰  (N⁰)

wherein X^(n0) is H, Cl, or F; Rf^(n0) is a linear, branched, or cyclicalkylene group having 3 to 20 carbon atoms in which some or all of H arereplaced by F; the alkylene group optionally containing one or moreether bonds in which some of H are replaced by Cl; and Y⁰ is an anionicgroup.

The anionic group Y⁰ may be —COOM, —SO₂M, or —SO₃M, and may be —COOM or—SO₃M.

M is H, a metal atom, NR⁷ ₄, imidazolium optionally having asubstituent, pyridinium optionally having a substituent, or phosphoniumoptionally having a substituent, wherein R⁷ is H or an organic group.

Examples of the metal atom include alkali metals (Group 1) and alkalineearth metals (Group 2), such as Na, K, or Li.

R⁷ may be H or a C₁₋₁₀ organic group, may be H or a C₁₋₄ organic group,and may be H or a C₁₋₄ alkyl group.

M may be H, a metal atom, or NR⁷ ₄, may be H, an alkali metal (Group 1),an alkaline earth metal (Group 2), or NR⁷ ₄, and may be H, Na, K, Li, orNH₄.

Rf^(n0) may be one in which 50% or more of H has been replaced byfluorine.

Examples of the compound represented by the general formula (N⁰)include:

a compound represented by the following general formula (N¹):X^(n0)—(CF₂)_(m1)—Y⁰  (N¹)

wherein X^(n0) is H, Cl, and F; m1 is an integer of 3 to 15; and Y⁰ isas defined above;

a compound represented by the following general formula (N²):Rf^(n1)—O—(CF(CF₃)CF₂O)_(m2)CFX^(n1)—Y⁰  (N²)

wherein Rf^(n1) is a perfluoroalkyl group having 1 to 5 carbon atoms; m2is an integer of 0 to 3; X^(n1) is F or CF₃; and Y⁰ is as defined above;

a compound represented by the following general formula (N³)Rf^(n2)(CH₂)_(m3)—(R^(fn3))_(q)—Y⁰  (N³)

wherein Rf^(n2) is a partially or fully fluorinated alkyl group having 1to 13 carbon atoms and optionally containing an ether bond; m3 is aninteger of 1 to 3; Rf^(n3) is a linear or branched perfluoroalkylenegroup having 1 to 3 carbon atoms; q is 0 or 1; and Y⁰ is as definedabove;

a compound represented by the following general formula (N⁴):Rf^(n4)—O—(CY^(n1)Y^(n2))_(p)CF₂—Y⁰  (N⁴)

wherein Rf^(n4) is a linear or branched partially or fully fluorinatedalkyl group having 1 to 12 carbon atoms and optionally containing anether bond; and Y^(n1) and Y^(n2) are the same or different and are eachH or F; p is 0 or 1; and Y⁰ is as defined above; and

a compound represented by the following general formula (N⁵).

wherein X^(n2), X^(n3), and X^(n4) may be the same or different and areeach H, F, or a linear or branched partially or fully fluorinated alkylgroup having 1 to 6 carbon atoms and optionally containing an etherbond; Rf^(n5) is a linear or branched partially or fully fluorinatedalkylene group having 1 to 3 carbon atoms and optionally containing anether bond; L is a linking group; and Y⁰ is as defined above, with theproviso that the total carbon number of X^(n2), X^(n3), X^(n4), andRf^(n5) is 18 or less.

More specific examples of the compound represented by the above generalformula (N⁰) include a perfluorocarboxylic acid (I) represented by thefollowing general formula (I), an ω-H perfluorocarboxylic acid (II)represented by the following general formula (II), aperfluoropolyethercarboxylic acid (III) represented by the followinggeneral formula (III), a perfluoroalkylalkylenecarboxylic acid (IV)represented by the following general formula (IV), aperfluoroalkoxyfluorocarboxylic acid (V) represented by the followinggeneral formula (V), a perfluoroalkylsulfonic acid (VI) represented bythe following general formula (VI), an ω-H perfluorosulfonic acid (VII)represented by the following general formula (VII), aperfluoroalkylalkylene sulfonic acid (VIII) represented by the followinggeneral formula (VIII), an alkylalkylene carboxylic acid (IX)represented by the following general formula (IX), a fluorocarboxylicacid (X) represented by the following general formula (X), analkoxyfluorosulfonic acid (XI) represented by the following generalformula (XI), and a compound (XII) represented by the following generalformula (XII).

The perfluorocarboxylic acid (I) is represented by the following generalformula (I):F(CF₂)_(n1)COOM  (I)

wherein n1 is an integer of 3 to 14; and M is H, a metal atom, NR⁷ ₄,imidazolium optionally having a substituent, pyridinium optionallyhaving a substituent, or phosphonium optionally having a substituent,wherein R⁷ is H or an organic group.

The ω-H perfluorocarboxylic acid (II) is represented by the followinggeneral formula (II):H(CF₂)_(n2)COOM  (II)

wherein n2 is an integer of 4 to 15; and M is as defined above.

The perfluoropolyethercarboxylic acid (III) is represented by thefollowing general formula (III):Rf¹—O—(CF(CF₃)CF₂O)_(n3)CF(CF₃)COOM  (III)

wherein Rf¹ is a perfluoroalkyl group having 1 to 5 carbon atoms; n3 isan integer of 0 to 3; and M is as defined above.

The perfluoroalkylalkylenecarboxylic acid (IV) is represented by thefollowing general formula (IV):Rf²(CH₂)_(n4)Rf³COOM  (IV)

wherein Rf² is a perfluoroalkyl group having 1 to 5 carbon atoms; Rf³ isa linear or branched perfluoroalkylene group having 1 to 3 carbon atoms;n4 is an integer of 1 to 3; and M is as defined above.

The alkoxyfluorocarboxylic acid (V) is represented by the followinggeneral formula (V):Rf⁴—O—CY¹Y²CF₂—COOM  (V)

wherein Rf⁴ is a linear or branched partially or fully fluorinated alkylgroup having 1 to 12 carbon atoms and optionally containing an etherbond; Y¹ and Y² are the same or different and are each H or F; and M isas defined above.

The perfluoroalkylsulfonic acid (VI) is represented by the followinggeneral formula (VI):F(CF₂)_(n5)SO₃M  (VI)

wherein n5 is an integer of 3 to 14; and M is as defined above.

The ω-H perfluorosulfonic acid (VII) is represented by the followinggeneral formula (VII):H(CF₂)_(n6)SO₃M  (VII)

wherein n6 is an integer of 4 to 14; and M is as defined above.

The perfluoroalkylalkylenesulfonic acid (VIII) is represented by thefollowing general formula (VIII):Rf⁵(CH₂)_(n7)SO₃M  (VIII)

wherein Rf⁵ is a perfluoroalkyl group having 1 to 13 carbon atoms; n7 isan integer of 1 to 3; and M is as defined above.

The alkylalkylenecarboxylic acid (IX) is represented by the followinggeneral formula (IX):Rf⁶(CH₂)_(n8)COOM  (IX)

wherein Rf⁶ is a linear or branched partially or fully fluorinated alkylgroup having 1 to 13 carbon atoms and optionally containing an etherbond; n8 is an integer of 1 to 3; and M is as defined above.

The fluorocarboxylic acid (X) is represented by the following generalformula (X):Rf⁷—O—Rf⁸—O—CF₂—COOM  (X)

wherein Rf⁷ is a linear or branched partially or fully fluorinated alkylgroup having 1 to 6 carbon atoms and optionally containing an etherbond; Rf⁸ is a linear or branched partially or fully fluorinated alkylgroup having 1 to 6 carbon atoms; and M is as defined above.

The alkoxyfluorosulfonic acid (XI) is represented by the followinggeneral formula (XI):Rf⁹—O—CY¹Y²CF₂—SO₃M  (XI)

wherein Rf⁹ is a linear or branched partially or fully fluorinated alkylgroup having 1 to 12 carbon atoms and optionally containing an etherbond and optionally containing chlorine; Y¹ and Y² are the same ordifferent and are each H or F; and M is as defined above.

The compound (XII) is represented by the following general formula(XII):

wherein X¹, X², and X³ may be the same or different and are H, F, and alinear or branched partially or fully fluorinated alkyl group having 1to 6 carbon atoms and optionally containing an ether bond; Rf¹⁰ is aperfluoroalkylene group having 1 to 3 carbon atoms; L is a linkinggroup; and Y⁰ is an anionic group.

Y⁰ may be —COOM, —SO₂M, or —SO₃M, and may be —SO₃M or COOM, where M isas defined above.

Examples of L include a single bond, a partially or fully fluorinatedalkylene group having 1 to 10 carbon atoms and optionally containing anether bond.

As described above, examples of the anionic fluorine-containingsurfactant include a carboxylic acid-based surfactant and a sulfonicacid-based surfactant.

The polymerization initiator may be any polymerization initiator capableof generating radicals within the polymerization temperature range, andknown oil-soluble and/or water-soluble polymerization initiators may beused. The polymerization initiator may be combined with a reducingagent, for example, to form a redox agent, which initiates thepolymerization. The concentration of the polymerization initiator isappropriately determined depending on the types of the monomers, themolecular weight of the target fluoropolymer, and the reaction rate.

The polymerization initiator to be used may be an oil-soluble radicalpolymerization initiator or a water-soluble radical polymerizationinitiator.

The oil-soluble radical polymerization initiator may be a knownoil-soluble peroxide, and representative examples thereof includedialkyl peroxycarbonates such as diisopropyl peroxydicarbonate anddi-sec-butyl peroxydicarbonate; peroxy esters such as t-butylperoxyisobutyrate and t-butyl peroxypivalate; and dialkyl peroxides suchas di-t-butyl peroxide, as well as di[perfluoro (or fluorochloro) acyl]peroxides such as di(ω-hydro-dodecafluoroheptanoyl)peroxide,di(ω-hydro-tetradecafluoroheptanoyl)peroxide,di(ω-hydro-hexadecafluorononanoyl)peroxide,di(perfluorobutyryl)peroxide, di(perfluorovaleryl)peroxide,di(perfluorohexanoyl)peroxide, di(perfluoroheptanoyl)peroxide,di(perfluorooctanoyl)peroxide, di(perfluorononanoyl)peroxide,di(ω-chloro-hexafluorobutyryl)peroxide,di(ω-chloro-decafluorohexanoyl)peroxide,di(ω-chloro-tetradecafluorooctanoyl)peroxide,ω-hydro-dodecafluoroheptanoyl-ω-hydrohexadecafluorononanoyl-peroxide,ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide,ω-hydrododecafluoroheptanoyl-perfluorobutyryl-peroxide,di(dichloropentafluorobutanoyl)peroxide,di(trichlorooctafluorohexanoyl)peroxide,di(tetrachloroundecafluorooctanoyl)peroxide,di(pentachlorotetradecafluorodecanoyl)peroxide, anddi(undecachlorodotoriacontafluorodocosanoyl)peroxide.

The water-soluble radical polymerization initiator may be a knownwater-soluble peroxide, and examples thereof include ammonium salts,potassium salts, and sodium salts of persulfuric acid, perchloric acid,and percarbonic acid, t-butyl permaleate, and t-butyl hydroperoxide. Areducing agent may also be contained together, and the use amountthereof may be 0.1 to 20 times that of the peroxide.

For example, in a case where the polymerization is performed at a lowtemperature of 30° C. or lower, the polymerization initiator used ispreferably a redox initiator obtained by combining an oxidizing agentand a reducing agent. Examples of the oxidizing agent includepersulfates, organic peroxides, potassium permanganate, manganesetriacetate, and ammonium cerium nitrate.

Examples of the reducing agent include bromates, diimines, and oxalicacid. Examples of the persulfates include ammonium persulfate andpotassium persulfate. In order to increase the decomposition rate of theinitiator, the combination of the redox initiator may preferably containa copper salt or an iron salt. An example of the copper salt iscopper(II) sulfate and an example of the iron salt is iron(II) sulfate.

Examples of the redox initiator include potassium permanganate/oxalicacid, manganese triacetate/oxalic acid, and cerium ammoniumnitrate/oxalic acid, and potassium permanganate/oxalic acid ispreferred. In the case of using a redox initiator, either an oxidizingagent or a reducing agent may be charged into a polymerization tank inadvance, followed by adding the other continuously or intermittentlythereto to initiate the polymerization. For example, in the case ofusing potassium permanganate/oxalic acid, preferably, oxalic acid ischarged into a polymerization tank and potassium permanganate iscontinuously added thereto.

The polymerization initiator may be added in any amount, and theinitiator in an amount that does not significantly decrease thepolymerization rate (e.g., several ppm in water) or more may be addedall at once in the initial stage of polymerization, or may be addedsequentially or continuously. The upper limit thereof falls within arange where the reaction temperature is allowed to increase while thepolymerization reaction heat is removed through the device surfaces. Theupper limit thereof is more preferably within a range where thepolymerization reaction heat can be removed through the device surfaces.

The aqueous medium is a reaction medium in which the polymerization isperformed, and means a liquid containing water. The aqueous medium maybe any medium containing water, and it may be one containing water and,for example, any of fluorine-free organic solvents such as alcohols,ethers, and ketones, and/or fluorine-containing organic solvents havinga boiling point of 40° C. or lower.

In the polymerization, known chain transfer agents, radical scavengers,and decomposers may be added to adjust the polymerization rate and themolecular weight depending on the purpose.

Examples of the chain transfer agent include esters such as dimethylmalonate, diethyl malonate, methyl acetate, ethyl acetate, butylacetate, and dimethyl succinate, as well as isopentane, methane, ethane,propane, methanol, isopropanol, acetone, various mercaptans, varioushalogenated hydrocarbons such as carbon tetrachloride, and cyclohexane.

The chain transfer agent to be used may be a bromine compound or aniodine compound. An example of a polymerization method using a brominecompound or an iodine compound is a method of performing polymerizationof a fluoromonomer in an aqueous medium substantially in the absence ofoxygen and in the presence of a bromine compound or an iodine compound(iodine transfer polymerization). Representative examples of the brominecompound or the iodine compound to be used include compounds representedby the general formula:R^(a)I_(x)Br_(y)

wherein x and y are each an integer of 0 to 2 and satisfy 1≤x+y≤2; andR^(a) is a saturated or unsaturated fluorohydrocarbon orchlorofluorohydrocarbon group having 1 to 16 carbon atoms, or ahydrocarbon group having 1 to 3 carbon atoms, each of which optionallycontains an oxygen atom. By using a bromine compound or an iodinecompound, iodine or bromine is introduced into the polymer, and servesas a crosslinking point.

Examples of the iodine compound include 1,3-diiodoperfluoropropane,2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane,1,4-diiodoperfluorobutane, 1,5-diiodo-2,4-dichloroperfluoropentane,1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane,1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane,diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n-propane, CF₂Br₂,BrCF₂CF₂Br, CF₃CFBrCF₂Br, CFClBr₂, BrCF₂CFClBr, CFBrClCFClBr,BrCF₂CF₂CF₂Br, BrCF₂CFBrOCF₃, 1-bromo-2-iodoperfluoroethane,1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane,2-bromo-3-iodoperfluorobutane,3-bromo-4-iodoperfluorobutene-1,2-bromo-4-iodoperfluorobutene-1, and amonoiodo- and monobromo-substitution product, diiodo- andmonobromo-substitution product, and (2-iodoethyl)- and(2-bromoethyl)-substitution product of benzene. These compounds may beused alone or in any combination.

Of these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and2-iodoperfluoropropane are preferably used from the viewpoints ofpolymerization reactivity, crosslinkability, availability, and the like.

The amount of the chain transfer agent used is usually 1 to 50,000 ppm,preferably 1 to 20,000 ppm, based on the total amount of thefluoromonomer fed.

The chain transfer agent may be added to the reaction vessel at oncebefore initiation of the polymerization, may be added at once afterinitiation of the polymerization, may be added in multiple portionsduring the polymerization, or may be added continuously during thepolymerization.

The method for producing a fluoropolymer may be a method for producing afluoropolymer including: (I) polymerizing the fluoromonomer in anaqueous medium in the presence of the surfactant to provide an aqueousdispersion of particles of a fluorine-containing polymer (A); and (II)seed-polymerizing the fluoromonomer to the particles of thefluorine-containing polymer (A) in the aqueous dispersion of theparticles of the fluorine-containing polymer (A).

Examples of the fluoropolymer suitably produced by the production methodof the present invention include a TFE polymer in which TFE is themonomer having the highest mole fraction (hereinafter, “most abundantmonomer”) among the monomers in the polymer, a VDF polymer in which VDFis the most abundant monomer, and a CTFE polymer in which CTFE is themost abundant monomer.

The TFE polymer may suitably be a TFE homopolymer, or may be a copolymercontaining (1) TFE, (2) one or two or more fluorine-containing monomerseach of which is different from TFE and has 2 to 8 carbon atoms, inparticular VDF, HFP, or CTFE, and (3) another monomer. Examples of (3)the another monomer include fluoro(alkyl vinyl ethers) having an alkylgroup having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms;fluorodioxoles; perfluoroalkyl ethylenes; and ω-hydroperfluoroolefins.

The TFE polymer may also be a copolymer of TFE and one or two or morefluorine-free monomers. Examples of the fluorine-free monomers includealkenes such as ethylene and propylene; vinyl esters; and vinyl ethers.The TFE polymer may also be a copolymer of TFE, one or two or morefluorine-containing monomers having 2 to 8 carbon atoms, and one or twoor more fluorine-free monomers.

The VDF polymer may suitably be a VDF homopolymer (PVDF), or may be acopolymer containing (1) VDF, (2) one or two or more fluoroolefins eachof which is different from VDF and has 2 to 8 carbon atoms, inparticular TFE, HFP, or CTFE, and (3) a perfluoro(alkyl vinyl ether)having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3carbon atoms, or the like.

The CTFE polymer may suitably be a CTFE homopolymer, or may be acopolymer containing (1) CTFE, (2) one or two or more fluoroolefins eachof which is different from CTFE and has 2 to 8 carbon atoms, inparticular TFE or HFP, and (3) a perfluoro(alkyl vinyl ether) having analkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbonatoms.

The CTFE polymer may also be a copolymer of CTFE and one or two or morefluorine-free monomers, and examples of the fluorine-free monomersinclude alkenes such as ethylene and propylene; vinyl esters; and vinylethers.

The fluoropolymer produced by the production method of the presentinvention may be vitreous, plastic, or elastomeric. The fluoropolymer isamorphous or partially crystallized, and may be subjected to compressionfiring, melt fabrication, or non-melt fabrication.

The production method of the present invention can suitably provide (I)non melt-processible fluororesins, including tetrafluoroethylenepolymers (TFE polymers (PTFE)); (II) melt-fabricable fluororesins,including ethylene/TFE copolymers (ETFE), TFE/HFP copolymers (FEP),TFE/perfluoro(alkyl vinyl ether) copolymers (e.g., PFA, MFA), TFE/VDFcopolymers, and electrolyte polymer precursors; and (III)fluoroelastomers, including TFE/propylene copolymers,TFE/propylene/third monomer copolymers (the third monomer may be VDF,HFP, CTFE, fluoroalkyl vinyl ether, or the like), TFE/fluoroalkyl vinylether copolymers; HFP/ethylene copolymers, HFP/ethylene/TFE copolymers;PVDF; thermoplastic elastomers such as VDF/HFP copolymers, HFP/ethylenecopolymers, and VDF/TFE/HFP copolymers; and fluorine-containingsegmented polymers disclosed in Japanese Patent Publication No.61-49327.

The fluoropolymer is preferably a fluororesin, more preferably afluororesin having a fluorine substitution percentage, calculated by thefollowing formula, of 50% or higher, still more preferably a fluororesinhaving the fluorine substitution percentage of higher than 50%, furtherpreferably a fluororesin having the fluorine substitution percentage of55% or higher, further preferably a fluororesin having the fluorinesubstitution percentage of 60% or higher, further preferably afluororesin having the fluorine substitution percentage of 75% orhigher, particularly preferably a fluororesin having the fluorinesubstitution percentage of 80% or higher, and most preferably afluororesin having the fluorine substitution percentage of 90 to 100%,i.e., a perfluororesin.Fluorine substitution percentage (%)=(number of fluorine atoms bonded tocarbon atoms constituting fluoropolymer)/((number of hydrogen atomsbonded to carbon atoms constituting fluoropolymer)+(number of fluorineatoms and chlorine atoms bonded to carbon atoms constitutingfluoropolymer))×100  (Formula)

The perfluororesin is more preferably a fluororesin having the fluorinesubstitution percentage of 95 to 100%, still more preferably PTFE, FEP,or PFA, and particularly preferably PTFE.

The fluoropolymer may have a core-shell structure. An example of thefluoropolymer having a core-shell structure is a modified PTFE includinga core of high-molecular-weight PTFE and a shell of alower-molecular-weight PTFE or a modified PTFE in the particle. Anexample of such a modified PTFE is PTFE disclosed in NationalPublication of International Patent Application No. 2005-527652.

The core-shell structure may have the following structures.

Core: TFE homopolymer Shell: TFE homopolymer

Core: modified PTFE Shell: TFE homopolymer

Core: modified PTFE Shell: modified PTFE

Core: TFE homopolymer Shell: modified PTFE

Core: low-molecular-weight PTFE Shell: high-molecular-weight PTFE

Core: high-molecular-weight PTFE Shell: low-molecular-weight PTFE

In the fluoropolymer having a core-shell structure, the lower limit ofthe proportion of the core is preferably 0.5% by mass, more preferably1.0% by mass, still more preferably 3.0% by mass, particularlypreferably 5.0% by mass, and most preferably 10.0% by mass. The upperlimit of the proportion of the core is preferably 99.5% by mass, morepreferably 99.0% by mass, still more preferably 98.0% by mass, furtherpreferably 97.0% by mass, particularly preferably 95.0% by mass, andmost preferably 90.0% by mass.

In the fluoropolymer having a core-shell structure, the lower limit ofthe proportion of the shell is preferably 0.5% by mass, more preferably1.0% by mass, still more preferably 3.0% by mass, particularlypreferably 5.0% by mass, and most preferably 10.0% by mass. The upperlimit of the proportion of the shell is preferably 99.5% by mass, morepreferably 99.0% by mass, still more preferably 98.0% by mass, furtherpreferably 97.0% by mass, particularly preferably 95.0% by mass, andmost preferably 90.0% by mass.

In the fluoropolymer having a core-shell structure, the core or theshell may be composed of two or more layers. For example, thefluoropolymer may have a trilayer structure including a core centerportion of a modified PTFE, a core outer layer portion of a TFEhomopolymer, and a shell of a modified PTFE.

Examples of the fluoropolymer having a core-shell structure also includethose in which a single particle of the fluoropolymer has a plurality ofcores.

(I) The non melt-processible fluororesins, (II) the melt-fabricablefluororesins, and (III) the fluoroelastomers suitably produced by theproduction method of the present invention are preferably produced inthe following manner.

(I) Non Melt-Processible Fluororesins

In the production method of the present invention, polymerization of TFEis usually performed at a polymerization temperature of 10 to 150° C.and a polymerization pressure of 0.05 to 5 MPaG. For example, thepolymerization temperature is more preferably 30° C. or higher, andstill more preferably 50° C. or higher. Further, the polymerizationtemperature is more preferably 120° C. or lower, and still morepreferably 100° C. or lower. Further, the polymerization pressure ismore preferably 0.3 MPaG or higher, still more preferably 0.5 MPaG orhigher, and more preferably 5.0 MPaG or lower, still more preferably 3.0MPaG or lower. In particular, from the viewpoint of improving the yieldof fluoropolymer, the polymerization pressure is preferably 1.0 MPaG ormore, more preferably 1.2 MPaG or more, still more preferably 1.5 MPaGor more, and more preferably 2.0 MPaG or more.

In an embodiment, the polymerization reaction is initiated by chargingpure water into a pressure-resistant reaction vessel equipped with astirrer, deoxidizing the system, charging TFE, increasing thetemperature to a predetermined level, and adding a polymerizationinitiator. When the pressure decreases as the reaction progresses,additional TFE is fed continuously or intermittently to maintain theinitial pressure. When the amount of TFE fed reaches a predeterminedlevel, feeding is stopped, and then TFE in the reaction vessel is purgedand the temperature is returned to room temperature, whereby thereaction is completed. Additional TFE may be added continuously orintermittently to prevent pressure drop.

In production of the TFE polymer (PTFE), various known modifyingmonomers may be used in combination. The TFE polymer as used herein is aconcept that encompasses not only a TFE homopolymer but also a nonmelt-processible copolymer of TFE and a modifying monomer (hereinafter,referred to as a “modified PTFE”).

The TFE polymer (PTFE) preferably has polymerized units derived from themodifying monomer (hereinafter, also referred to as “modifying monomerunit”) in the range of 0.00001 to 1.0% by mass. The lower limit of themodifying monomer unit is more preferably 0.0001% by mass, still morepreferably 0.001% by mass, further preferably 0.005% by mass, andparticularly preferably 0.009% by mass. The upper limit of the modifyingmonomer unit is preferably 0.90% by mass, more preferably 0.50% by mass,still more preferably 0.40% by mass, further preferably 0.30% by mass,still further preferably 0.10% by mass, and particularly preferably0.05% by mass.

The modifying monomer unit as used herein means a portion of themolecular structure of the TFE polymer as a part derived from themodifying monomer.

Examples of the modifying monomer include perhaloolefins such as HFP andCTFE; fluoro(alkyl vinyl ethers) having an alkyl group having 1 to 5carbon atoms, particularly 1 to 3 carbon atoms; cyclic fluorinatedmonomers such as fluorodioxole; perhaloalkyl ethylenes; andω-hydroperhaloolefins. The modifying monomer may be added all at once inthe initial stage, or may be added continuously or intermittently inportions depending the purpose and the manner of TFE feeding.

The modifying monomer is also preferably exemplified by a comonomer (3)having a monomer reactivity ratio of 0.1 to 8. The presence of thecomonomer (3) makes it possible to obtain modified PTFE particles havinga small particle size, and to thereby obtain an aqueous dispersionhaving high dispersion stability.

Here, the monomer reactivity ratio in copolymerization with TFE is avalue obtained by dividing the rate constant in the case thatpropagating radicals react with TFE by the rate constant in the casethat the propagating radicals react with comonomers, in the case thatthe propagating radicals are less than the repeating unit derived fromTFE. A smaller monomer reactivity ratio indicates higher reactivity ofthe comonomers with TFE. The monomer reactivity ratio can be calculatedby determining the compositional features of the polymer producedimmediately after the initiation of copolymerization of TFE andcomonomers and using the Fineman-Ross equation.

The copolymerization is performed using 3,600 g of deionized degassedwater, 1,000 ppm of ammonium perfluorooctanoate based on the water, and100 g of paraffin wax contained in an autoclave made of stainless steelwith an internal volume of 6.0 L at a pressure of 0.78 MPa and atemperature of 70° C. A comonomer in an amount of 0.05 g, 0.1 g, 0.2 g,0.5 g, or 1.0 g is added into the reactor, and then 0.072 g of ammoniumpersulfate (20 ppm based on the water) is added thereto. To maintain thepolymerization pressure at 0.78 MPa, TFE is continuously fed thereinto.When the charged amount of TFE reaches 1,000 g, stirring is stopped andthe pressure is released until the pressure in the reactor decreases tothe atmospheric pressure. After cooling, the paraffin wax is separatedto obtain an aqueous dispersion containing the resulting polymer. Theaqueous dispersion is stirred so that the resulting polymer coagulates,and the polymer is dried at 150° C. The compositional features in theresulting polymer are calculated by appropriate combination of NMR,FT-IR, elemental analysis, and X-ray fluorescence analysis depending onthe types of the monomers.

The comonomer (3) having a monomer reactivity ratio of 0.1 to 8 ispreferably at least one selected from the group consisting of comonomersrepresented by the formulas (3a) to (3d):CH₂═CH—Rf¹  (3a)

wherein Rf¹ is a perfluoroalkyl group having 1 to 10 carbon atoms;CF₂═CF—O—Rf²  (3b)wherein Rf² is a perfluoroalkyl group having 1 to 2 carbon atoms;CF₂═CF—O—(CF₂)_(n)CF═CF₂  (3c)

wherein n is 1 or 2; and

wherein X³ and X⁴ are each F, Cl, or a methoxy group; and Y isrepresented by the formula Y1 or Y2;

in the formula Y2, Z and Z′ are each F or a fluorinated alkyl grouphaving 1 to 3 carbon atoms.

The content of the comonomer (3) is preferably in the range of 0.00001to 1.0% by mass with respect to the modified PTFE. The lower limitthereof is more preferably 0.0001% by mass, still more preferably 0.001%by mass, further preferably 0.005% by mass, and particularly preferably0.009% by mass. The upper limit thereof is more preferably 0.50% bymass, still more preferably 0.40% by mass, further preferably 0.30% bymass, still further preferably 0.10% by mass, and particularlypreferably 0.05% by mass.

The modifying monomer is preferably at least one selected from the groupconsisting of hexafluoropropylene, vinylidene fluoride, fluoro(alkylvinyl ether), (perfluoroalkyl)ethylene, ethylene, and modifying monomershaving a functional group capable of reacting by radical polymerizationand a hydrophilic group, in view of obtaining an aqueous dispersion ofpolytetrafluoroethylene particles having a small average primaryparticle size, a small aspect ratio, and excellent stability.

From the viewpoint of reactivity with TFE, the modifying monomerpreferably contains at least one selected from the group consisting ofhexafluoropropylene, perfluoro(alkyl vinyl ether), and(perfluoroalkyl)ethylene.

More preferably, the modifying monomer contains at least one selectedfrom the group consisting of hexafluoropropylene, perfluoro(methyl vinylether), perfluoro(propyl vinyl ether), (perfluorobutyl)ethylene,(perfluorohexyl)ethylene, and (perfluorooctyl)ethylene.

The total amount of the hexafluoropropylene unit, perfluoro(alkyl vinylether) unit and (perfluoroalkyl)ethylene unit is preferably in the rangeof 0.00001 to 1.0% by mass based on the modified PTFE.

The lower limit of the total amount thereof is more preferably 0.001% bymass, still more preferably 0.005% by mass, and particularly preferably0.009% by mass. The upper limit thereof is more preferably 0.50% bymass, still more preferably 0.40% by mass, further preferably 0.30% bymass, still further preferably 0.10% by mass, and particularlypreferably 0.05% by mass.

In the production method of the present invention, a modifying monomerhaving a functional group capable of reacting by radical polymerizationand a hydrophilic group (hereinafter referred to as “modifying monomer(A)”) may be used together with the surfactant. The modifying monomer(A) may be a compound containing at least one vinyl group and having asurfactant function. Examples of the hydrophilic group in the modifyingmonomer (A) include —NH₂, —PO₃M, —OPO₃M, —SO₃M, —OSO₃M, and —COOM,wherein M represents H, a metal atom, NR⁷ ₄, imidazolium optionallyhaving a substituent, pyridinium optionally having a substituent, orphosphonium optionally having a substituent, wherein R⁷ is H or anorganic group, and may be the same or different, and any two thereof maybe bonded to each other to form a ring. Of these, the hydrophilic groupis preferably —SO₃M or —COOM. R⁷ is preferably H or a C₁₋₁₀ organicgroup, more preferably H or a C₁₋₄ organic group, and still morepreferably H or a C₁₋₄ alkyl group.

Examples of the metal atom include monovalent and divalent metal atoms,alkali metals (Group 1) and alkaline earth metals (Group 2), andpreferred is Na, K, or Li.

Examples of the “functional group capable of reacting by radicalpolymerization” in the modifying monomer (A) include groups having anethylenically unsaturated bond. Examples of the group having anethylenically unsaturated bond include a linking group as R^(a)described later. Preferred are groups having an unsaturated bond, suchas —CH═CH₂, —CF═CH₂, —CH═CF₂, —CF═CF₂, —CH₂—CH═CH₂, —CF₂—CF═CH₂,—CF₂—CF═CF₂, —(C═O)—CH═CH₂, —(C═O)—CF═CH₂, —(C═O)—CH═CF₂, —(C═O)—CF═CF₂,—(C═O)—C(CH₃)═CH₂, —(C═O)—C(CF₃)═CH₂, —(C═O)—C(CH₃)═CF₂,—(C═O)—C(CF₃)═CF₂, —O—CH₂—CH═CH₂, —O—CF₂—CF═CH₂, —O—CH₂—CH═CF₂, and—O—CF₂—CF═CF₂.

The modifying monomer (A) is preferably a compound represented by thegeneral formula (4):CX^(i)X^(k)═CX^(j)R^(a)—(CZ¹Z²)_(k)—Y³  (4)

wherein X^(i), X^(j), and X^(k) are each independently F, Cl, H, or CF₃;Y³ is a hydrophilic group; R^(a) is a linking group; Z¹ and Z² are eachindependently H, F, or CF₃; and k is 0 or 1.

Examples of the hydrophilic group include —NH₂, —PO₃M, —OPO₃M, —SO₃M,—OSO₃M, and —COOM, wherein M represents H, a metal atom, NR⁷ ₄,imidazolium optionally having a substituent, pyridinium optionallyhaving a substituent, or phosphonium optionally having a substituent,wherein R⁷ is H or an organic group, and may be the same or different,and any two thereof may be bonded to each other to form a ring. Ofthese, the hydrophilic group is preferably —SO₃M or —COOM. R⁷ ispreferably H or a C₁₋₁₀ organic group, more preferably H or a C₁₋₄organic group, and still more preferably H or a C₁₋₄ alkyl group.

Examples of the metal atom include monovalent and divalent metal atoms,alkali metals (Group 1) and alkaline earth metals (Group 2), andpreferred is Na, K, or Li.

The use of the modifying monomer (A) allows for obtaining an aqueousdispersion having a smaller average primary particle size and superiorstability. Also, the aspect ratio of the primary particles can be madesmaller.

R^(a) is a linking group. The “linking group” as used herein refers to adivalent linking group. The linking group may be a single bond andpreferably contains at least one carbon atom, and the number of carbonatoms may be 2 or more, 4 or more, 8 or more, 10 or more, or 20 or more.The upper limit thereof is not limited, but may be 100 or less, and maybe 50 or less, for example.

The linking group may be linear or branched, cyclic or acyclic,saturated or unsaturated, substituted or unsubstituted, and optionallycontains one or more heteroatoms selected from the group consisting ofsulfur, oxygen, and nitrogen, and optionally contains one or morefunctional groups selected from the group consisting of esters, amides,sulfonamides, carbonyls, carbonates, urethanes, ureas and carbamates.The linking group may be free from carbon atoms and may be a catenaryheteroatom such as oxygen, sulfur, or nitrogen.

R^(a) is preferably a catenary heteroatom such as oxygen, sulfur, ornitrogen, or a divalent organic group.

When R^(a) is a divalent organic group, the hydrogen atom bonded to thecarbon atom may be replaced by a halogen other than fluorine, such aschlorine, and may or may not contain a double bond. Further, R^(a) maybe linear or branched, and may be cyclic or acyclic. R^(a) may alsocontain a functional group (e.g., ester, ether, ketone, amine, halide,etc.).

R^(a) may also be a fluorine-free divalent organic group or a partiallyfluorinated or perfluorinated divalent organic group.

R^(a) may be, for example, a hydrocarbon group in which a fluorine atomis not bonded to a carbon atom, a hydrocarbon group in which some of thehydrogen atoms bonded to a carbon atom are replaced by fluorine atoms, ahydrocarbon group in which all of the hydrogen atoms bonded to thecarbon atoms are replaced by fluorine atoms, —(C═O)—, —(C═O)—O—, or ahydrocarbon group containing —(C═O)—, and these groups optionallycontain an oxygen atom, optionally contain a double bond, and optionallycontain a functional group.

R^(a) is preferably —(C═O)—, —(C═O)—O—, or a hydrocarbon group having 1to 100 carbon atoms that optionally contains an ether bond andoptionally contains a carbonyl group, wherein some or all of thehydrogen atoms bonded to the carbon atoms in the hydrocarbon group maybe replaced by fluorine.

R^(a) is preferably at least one selected from —(CH₂)_(a)—, —(CF₂)_(a)—,—O—(CF₂)_(a)—, —(CF₂)_(a)—O—(CF₂)_(b)—, —O(CF₂)_(a)—O—(CF₂)_(b)—,—(CF₂)_(a), —[O—(CF₂)_(b)]_(c)—, —O(CF₂)_(a)—[O—(CF₂)_(b)]_(c)—,—[(CF₂)_(a)—O]_(b)—[(CF₂)_(c)—O]_(d)—,—O[(CF₂)_(a)—O]_(b)—[(CF₂)_(c)—O]_(d)—, —O—[CF₂CF(CF₃)O]_(a)—(CF₂)_(b)—,—(C═O)—, —(C═O)—O—, —(C═O)—(CH₂)_(a)—, —(C═O)—(CF₂)_(a)—,—(C═O)—O—(CH₂)_(a)—, —(C═O)—O—(CF₂)_(a)—, —(C═O)—[(CH₂)_(a)—O]_(b)—,—(C═O)—[(CF₂)_(a)—O], —(C═O)—O[(CH₂)_(a)—O]_(b),—(C═O)—O[(CF₂)_(a)—O]_(b)—, —(C═O)—O[(CH₂)_(a)—O]_(b)—(CH₂)_(c)—,—(C═O)—O[(CF₂)_(a)—O]_(b)—(CF₂)_(c)—, —(C═O)—(CH₂)_(a)—O—(CH₂)_(b)—,—(C═O)—(CF₂)_(a)—O—(CF₂)_(b)—, —(C═O)—O—(CH₂)_(a)—O—(CH₂)_(b)—,—(C═O)—O—(CF₂)_(a)—O—(CF₂)_(b)—, —(C═O)—O—C₆H₄—, and combinationsthereof.

In the formula, a, b, c, and d are independently at least 1 or more. a,b, c and d may independently be 2 or more, 3 or more, 4 or more, 10 ormore, or 20 or more. The upper limits of a, b, c, and d are 100, forexample.

Specific examples suitable for R^(a) include —CF₂—O—, —CF₂—O—CF₂—,—CF₂—O—CH₂—, —CF₂—O—CH₂CF₂—, —CF₂—O—CF₂CF₂—, —CF₂—O—CF₂CH₂—,—CF₂—O—CF₂CF₂CH₂—, —CF₂—O—CF(CF₃)—, —CF₂—O—CF(CF₃)CF₂—,—CF₂—O—CF(CF₃)CF₂—O—, —CF₂—O—CF(CF₃)CH₂—, —(C═O)—, —(C═O)—O—,—(C═O)—(CH₂)—, —(C═O)—(CF₂)—, —(C═O)—O—(CH₂)—, —(C═O)—O—(CF₂)—,—(C═O)—[(CH₂)₂—O]_(n)—, —(C═O)—[(CF₂)₂—O]_(n)—, —(C═O)—O[(CH₂)₂—O]_(n)—,—(C═O)—O[(CF₂)₂—O]_(n)—, —(C═O)—O[(CH₂)₂—O]_(n)—(CH₂)—,—(C═O)—O[(CF₂)₂—O]_(n)—(CF₂)—, —(C═O)—(CH₂)₂—O—(CH₂)—,—(C═O)—(CF₂)₂—O—(CF₂)—, —(C═O)—O—(CH₂)₂—O—(CH₂)—,—(C═O)—O—(CF₂)₂—O—(CF₂)—, and —(C═O)—O—C₆H₄—. In particular, preferredfor R^(a) among these is —CF₂—O—, —CF₂—O—CF₂—, —CF₂—O—CF₂CF₂—,—CF₂—O—CF(CF₃)—, —CF₂—O—CF(CF₃)CF₂—, —CF₂—O—CF(CF₃)CF₂—O—, —(C═O)—,—(C═)—O—, —(C═O)—(CH₂)—, —(C═O)—O—(CH₂)—, —(C═O)—O[(CH₂)₂—O]_(n)—,—(C═O)—O[(CH₂)₂—O]_(n)—(CH₂)—, —(C═O)—(CH₂)₂—O—(CH₂)—, or—(C═O)—O—C₆H₄—.

In the formula, n is an integer of 1 to 10.

—R^(a)—(CZ¹Z²)_(k) in the general formula (4) is preferably —CF₂—O—CF₂—,—CF₂—O—CF(CF₃)—, —CF₂—O—C(CF₃)₂—, —CF₂—O—CF₂—CF₂—, —CF₂—O—CF₂—CF(CF₃)—,—CF₂—O—CF₂—C(CF₃)₂—, —CF₂—O—CF₂CF₂—CF₂—, —CF₂—O—CF₂CF₂—CF(CF₃)—,—CF₂—O—CF₂CF₂—C(CF₃)₂—, —CF₂—O—CF(CF₃)—CF₂—, —CF₂—O—CF(CF₃)—CF(CF₃)—,—CF₂—O—CF(CF₃)—C(CF₃)₂—, —CF₂—O—CF(CF₃)—CF₂—, —CF₂—O—CF(CF₃)—CF(CF₃)—,—CF₂—O—CF(CF₃)—C(CF₃)₂—, —CF₂—O—CF(CF₃)CF₂—CF₂—,—CF₂—O—CF(CF₃)CF₂—CF(CF₃)—, —CF₂—O—CF(CF₃)CF₂—C(CF₃)₂—,—CF₂—O—CF(CF₃)CF₂—O—CF₂—, —CF₂—O—CF(CF₃)CF₂—O—CF(CF₃)—,—CF₂—O—CF(CF₃)CF₂—O—C(CF₃)₂—, —(C═O)—, —(C═O)—O—, —(C═O)—(CH₂)—,—(C═O)—(CF₂)—, —(C═O)—O—(CH₂)—, —(C═O)—O—(CF₂)—,—(C═O)—[(CH₂)₂—O]_(n)—(CH₂)—, —(C═O)—[(CF₂)₂—O]_(n)—(CF₂)—,—(C═O)—[(CH₂)₂—O]_(n)—(CH₂)—(CH₂)—, —(C═O)—[(CF₂)₂—O]_(n)—(CF₂)—(CF₂)—,—(C═O)—O[(CH₂)₂—O]_(n)—(CF₂)—, —(C═O)—O[(CH₂)₂—O]_(n)—(CH₂)—(CH₂)—,—(C═O)—O[(CF₂)₂—O]_(n)—(CF₂)—, —(C═O)—O[(CF₂)₂—O]_(n)—(CF₂)—(CF₂)—,—(C═O)—(CH₂)₂—O—(CH₂)—(CH₂)—, —(C═O)—(CF₂)₂—O—(CF₂)—(CF₂)—,—(C═O)—O—(CH₂)₂—O—(CH₂)—(CH₂)—, —(C═O)—O—(CF₂)₂—O—(CF₂)—(CF₂)—,—(C═O)—O—(CH₂)₂—O—(CH₂)—C(CF₃)₂—, —(C═O)—O—(CF₂)₂—O—(CF₂)—C(CF₃)₂—, or—(C═O)—O—C₆H₄—C(CF₃)₂—, and is more preferably —CF₂—O—CF(CF₃)—,—CF₂—O—CF₂—CF(CF₃)—, —CF₂—O—CF₂CF₂—CF(CF₃)—, —CF₂—O—CF(CF₃)—CF(CF₃)—,—CF₂—O—CF(CF₃)CF₂—CF(CF₃)—, —CF₂—O—CF(CF₃)CF₂—O—CF(CF₃)—, —(C═O)—,—(C═O)—O—(CH₂)—, —(C═O)—O—(CH₂)—(CH₂)—,—(C═O)—O[(CH₂)₂—O]_(n)—(CH₂)—(CH₂)—, —(C═O)—O—(CH₂)₂—O—(CH₂)—C(CF₃)₂—,or —(C═O)—O—C₆H₄—C(CF₃)₂—.

In the formula, n is an integer of 1 to 10.

Specific examples of the compound represented by the general formula (4)include compounds represented by the following formulas:

wherein X^(j) and Y³ are as described above; and n is an integer of 1 to10.

R^(a) is preferably a divalent group represented by the followinggeneral formula (r1):—(C═O)_(h)—(O)_(i)—CF₂—O—(CX⁶)_(e)—{O—CF(CF₃)}_(f)—(O)_(g)—  (r1)

wherein X⁶ is each independently H, F, or CF₃; e is an integer of 0 to3; f is an integer of 0 to 3; g is 0 or 1; h is 0 or 1; and i is 0 or 1,

and is also preferably a divalent group represented by the followinggeneral formula (r2):—(C═O)_(h)—(O)_(i)—CF₂—O—(CX⁷ ₂)_(e)—(O)_(g)—  (r2)

wherein X⁷ is each independently H, F, or CF₃; e is an integer of 0 to3; g is 0 or 1; h is 0 or 1; and i is 0 or 1.

—R^(a)—CZ¹Z²— in the general formula (4) is also preferably a divalentgroup represented by the following formula (t1):—(C═O)_(h)—(O)_(i)—CF₂—O—(CX⁶₂)_(e)—{O—CF(CF₃)}_(f)—(O)_(g)—CZ¹Z²—  (t1)

wherein X⁶ is each independently H, F, or CF₃; e is an integer of 0 to3; f is an integer of 0 to 3; g is 0 or 1; h is 0 or 1; i is 0 or 1; andZ¹ and Z² are each independently F or CF₃,

and is more preferably a group in which one of Z¹ and Z² is F and theother is CF₃ in the formula (t1)

Also, in the general formula (4), —R^(a)—CZ¹Z²— is preferably a divalentgroup represented by the following formula (t2):(C═O)_(h)—(O)_(i)—CF₂—O—(CX⁷ ₂)_(e)—(O)_(g)—CZ¹Z²—  (t2)

wherein X⁷ is each independently H, F, or CF₃; e is an integer of 0 to3; g is 0 or 1; h is 0 or 1; i is C or 1; and Z¹ and Z² are eachindependently H, F, or CF₃,

and is more preferably a group in which one of Z¹ and Z² is F and theother is CF₃ in the formula (t2).

The compound represented by the general formula (4) also preferably hasa C—F bond and does not have a C—H bond, in the portion excluding thehydrophilic group (Y³). In other words, in the general formula (4),X^(i), X^(j), and X^(k) are all F, and R^(a) is preferably aperfluoroalkylene group having 1 or more carbon atoms; theperfluoroalkylene group may be either linear or branched, may be eithercyclic or acyclic, and may contain at least one catenary heteroatom. Theperfluoroalkylene group may have 2 to 20 carbon atoms or 4 to 18 carbonatoms.

The compound represented by the general formula (4) may be partiallyfluorinated. In other words, the compound represented by the generalformula (4) also preferably has at least one hydrogen atom bonded to acarbon atom and at least one fluorine atom bonded to a carbon atom, inthe portion excluding the hydrophilic group (Y³).

The compound represented by the general formula (4) is also preferably acompound represented by the following formula (4a):CF₂═CF—O—Rf⁰—Y³  (4a)

wherein Y³ is a hydrophilic group; and Rf⁰ is a perfluorinated divalentlinking group which is perfluorinated and may be a linear or branched,cyclic or acyclic, saturated or unsaturated, substituted orunsubstituted, and optionally contains one or more heteroatoms selectedfrom the group consisting of sulfur, oxygen, and nitrogen.

The compound represented by the general formula (4) is also preferably acompound represented by the following formula (4b):CH₂═CH—O—Rf⁰—Y³  (4b)

wherein Y³ is a hydrophilic group; and Rf⁰ is a perfluorinated divalentlinking group as defined in the formula (4a).

In the general formula (4), Y³ is preferably —OSO₃M.

Examples of the polymerized units derived from the compound representedby the general formula (4) when Y³ is —OSO₃M include—[CF₂CF(OCF₂CF₂CH₂OSO₃M)]-, —[CH₂CH((CF₂)₄CH₂OSO₃M)]-,—[CF₂CF(O(CF₂)₄CH₂OSO₃M)]-, —[CF₂CF(OCF₂CF(CF₃)CH₂OSO₃M)]-,—[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂CH₂OSO₃M)]-, —[CH₂CH((CF₂)₄CH₂OSO₃M)]-,—[CF₂CF(OCF₂CF₂SO₂N(CH₃)CH₂CH₂OSO₃M)]-, —[CH₂CH(CF₂CF₂CH₂OSO₃M)]-,—[CF₂CF(OCF₂CF₂CF₂CF₂SO₂N(CH₃)CH₂CH₂OSO₃M)]-, and—[CH₂CH(CF₂CF₂CH₂OSO₃M)]-. In the formula, M is as described above.

In the general formula (4), Y³ is preferably —SO₃M. Examples of thepolymerized units derived from the compound represented by the generalformula (4) when Y³ is —SO₃M include —[CF₂CF(OCF₂CF₂SO₃M)]-,—[CF₂CF(O(CF₂)₄SO₃M)]-, —[CF₂CF(OCF₂CF(CF₃)SO₃M)]-, —[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂SO₃M)]-, —[CH₂CH(CF₂CF₂SO₃M)]-, —[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂CF₂CF₂SO₃M)]-, —[CH₂CH((CF₂)₄SO₃M)]-, —[CH₂CH(CF₂CF₂SO₃M)]-, and—[CH₂CH((CF₂)₄SO₃M)]-. In the formula, M is as described above.

In the general formula (4), Y³ is preferably —COOM. Examples of thepolymerized units derived from the compound represented by the generalformula (4) when Y³ is —COOM include —[CF₂CF(OCF₂CF₂COOM)]-,—[CF₂CF(O(CF₂)₅COOM)]-, —[CF₂CF(OCF₂CF(CF₃) COOM)]-,—[CF₂CF(OCF₂CF(CF₃)O(CF₂)_(n)COOM)]- (n is greater than 1),—[CH₂CH(CF₂CF₂COOM)]-, —[CH₂CH((CF₂)₄COOM)]-, —[CH₂CH(CF₂CF₂COOM)]-,—[CH₂CH((CF₂)₄COOM)]-, —[CF₂CF(OCF₂CF₂SO₂NR′CH₂COOM)]-,—[CF₂CF(O(CF₂)₄SO₂NR′CH₂COOM)]-, —[CF₂CF(OCF₂CF(CF₃)SO₂NR′CH₂COOM)]-,—[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂SO₂NR′CH₂COOM)]-,—[CH₂CH(CF₂CF₂SO₂NR′CH₂COOM)]-,—[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂CF₂CF₂SO₂NR′CH₂COOM)]-,—[CH₂CH((CF₂)₄SO₂NR′CH₂COOM)]-, —[CH₂CH(CF₂CF₂SO₂NR′CH₂COOM)]-, and—[CH₂CH((CF₂)₄SO₂NR′CH₂COOM)]-. In the formula, R′ is H or a C₁₋₄ alkylgroup, and M is as described above.

In the general formula (4), Y³ is preferably —OPO₃M.

Examples of the polymerized units derived from the compound representedby the general formula (4) when Y³ is —OPO₃M include—[CF₂CF(OCF₂CF₂CH₂OP(O)(OM)₂)]-, —[CF₂CF(O(CF₂)₄CH₂OP(O)(OM)₂)]-,—[CF₂CF(OCF₂CF(CF₃)CH₂OP(O) (OM)₂)]-, —[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂CH₂OP(O)(OM)₂)]-, —[CF₂CF(OCF₂CF₂SO₂N(CH₃) CH₂CH₂OP(O)(OM)₂)]-,—[CF₂CF(OCF₂CF₂CF₂CF₂SO₂N(CH₃) CH₂CH₂P(O(OM)₂)]-, —[CH₂CH(CF₂CF₂CH₂OP(O)(OM)₂)]-, —[CH₂CH((CF₂)₄CH₂OP(O)(OM)₂)]-, —[CH₂CH(CF₂CF₂CH₂OP(O)(OM)₂)]-, and —[CH₂CH((CF₂)₄CH₂OP(O)(OM)₂)]-. In the formula, M is asdescribed above.

In the general formula (4), Y³ is preferably —PO₃M.

Examples of the polymerized units derived from the compound representedby the general formula (4) when Y³ is —PO₃M include —[CF₂CF(OCF₂CF₂P(O)(OM)₂)]-, —[CF₂CF(O(CF₂)₄P(O(OM)₂)]-, —[CF₂CF(OCF₂CF(CF₃) P(O(OM)₂)]-,—[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂P(O) (OM)₂)]-, —[CH₂CH(CF₂CF₂P(O(OM)₂)]-,—[CH₂CH((CF₂)₄P(O(OM)₂)]-, —[CH₂CH(CF₂CF₂P(O(OM)₂)]-, and—[CH₂CH((CF₂)₄P(O(OM)₂)]-, wherein M is as described above.

The compound represented by the general formula (4) is preferably atleast one selected from the group consisting of:

a monomer represented by the following general formula (5):CX₂═CY(—CZ₂—O—Rf—Y³)  (5)

wherein X is the same or different and is —H or —F; Y is —H, —F, analkyl group, or a fluorine-containing alkyl group; Z is the same ordifferent and —H, —F, an alkyl group, or a fluorine-containing alkylgroup; Rf is a fluorine-containing alkylene group having 1 to 40 carbonatoms or a fluorine-containing alkylene group having 2 to 100 carbonatoms and having an ether bond; and Y³ is as described above;

a monomer represented by the following general formula (6):CX₂═CY(—O—Rf—Y³)  (6)

wherein X is the same or different and is —H or —F; Y is —H, —F, analkyl group, or a fluorine-containing alkyl group; Rf is afluorine-containing alkylene group having 1 to 40 carbon atoms or afluorine-containing alkylene group having 2 to 100 carbon atoms andhaving an ether bond; and Y³ is as described above; and

a monomer represented by the following general formula (7):CX₂═CY(—Rf—Y³)  (7)

wherein X is the same or different and is —H or —F; Y is —H, —F, analkyl group, or a fluorine-containing alkyl group; Rf is afluorine-containing alkylene group having 1 to 40 carbon atoms or afluorine-containing alkylene group having 2 to 100 carbon atoms andhaving an ether bond; and Y³ is as described above.

In the general formula (5), each X is —H or —F. X may be both —H, may beboth —F, or at least one thereof may be —H. For example, one thereof maybe —F and the other may be —H, or both may be —H.

In the general formula (5), Y is —H, —F, an alkyl group, or afluorine-containing alkyl group.

The alkyl group is an alkyl group free from fluorine atoms and may haveone or more carbon atoms. The alkyl group preferably has 6 or lesscarbon atoms, more preferably 4 or less carbon atoms, and still morepreferably 3 or less carbon atoms.

The fluorine-containing alkyl group is an alkyl group containing atleast one fluorine atom, and may have one or more carbon atoms. Thefluorine-containing alkyl group preferably has 6 or less carbon atoms,more preferably 4 or less carbon atoms, and still more preferably 3 orless carbon atoms.

Y is preferably —H, —F, or —CF₃, and more preferably —F.

In the general formula (5), Z is the same or different and is —H, —F, analkyl group, or a fluoroalkyl group.

The alkyl group is an alkyl group free from fluorine atoms and may haveone or more carbon atoms. The alkyl group preferably has 6 or lesscarbon atoms, more preferably 4 or less carbon atoms, and still morepreferably 3 or less carbon atoms.

The fluorine-containing alkyl group is an alkyl group containing atleast one fluorine atom, and may have one or more carbon atoms. Thefluorine-containing alkyl group preferably has 6 or less carbon atoms,more preferably 4 or less carbon atoms, and still more preferably 3 orless carbon atoms.

Z is preferably —H, —F, or —CF₃, and more preferably —F.

In the general formula (5), at least one of X, Y, and Z preferablycontains a fluorine atom. For example, X, Y, and Z may be —H, —F, and—F, respectively.

In the general formula (5), Rf is a fluorine-containing alkylene grouphaving 1 to 40 carbon atoms or a fluorine-containing alkylene grouphaving 2 to 100 carbon atoms and having an ether bond.

The fluorine-containing alkylene group preferably has 2 or more carbonatoms. The fluorine-containing alkylene group also preferably has 30 orless carbon atoms, more preferably 20 or less carbon atoms, and stillmore preferably 10 or less carbon atoms. Examples of thefluorine-containing alkylene group include —CF₂—, —CH₂CF₂—, —CF₂CF₂—,—CF₂CH₂—, —CF₂CF₂CH₂—, —CF(CF₃)—, —CF(CF₃)CF₂—, and —CF(CF₃)CH₂—. Thefluorine-containing alkylene group is preferably a perfluoroalkylenegroup.

The fluorine-containing alkylene group having an ether bond preferablyhas 3 or more carbon atoms. The fluorine-containing alkylene grouphaving an ether bond also preferably has 60 or less carbon atoms, morepreferably 30 or less carbon atoms, and still more preferably 12 or lesscarbon atoms.

For example, the fluorine-containing alkylene group having an ether bondis preferably a divalent group represented by the following formula:

wherein Z¹ is F or CF₃; Z² and Z³ are each H or F; Z⁴ is H, F, or CF₃;p1+q1+r1 is an integer of 0 to 10; s1 is 0 or 1; and t1 is an integer of0 to 5, with the proviso that when Z³ and Z⁴ are both H, p1+q1+r1+s1 isnot 0.

Specific examples of the fluorine-containing alkylene group having anether bond include —CF(CF₃)CF₂—O—CF(CF₃)—, —(CF(CF₃)CF₂—O)_(n)—CF(CF₃)—(where n is an integer of 1 to 10), —CF(CF₃)CF₂—O—CF(CF₃)CH₂—,—(CF(CF₃)CF₂—O)_(n)—CF(CF₃)CH₂— (where n is an integer of 1 to 10),—CH₂CF₂CF₂O—CH₂CF₂CH₂—, —CF₂CF₂CF₂O—CF₂CF₂—, —CF₂CF₂CF₂O—CF₂CF₂CH₂—,—CF₂CF₂O—CF₂—, —CF₂CF₂O—CF₂CH₂—, and —CF(CF₃)CH₂—.

The fluorine-containing alkylene group having an ether bond ispreferably a perfluoroalkylene group.

In the general formula (5), Y³ is —COOM, —SO₃M, or —OSO₃M, wherein M isH, a metal atom, NR⁷ ₄, imidazolium optionally having a substituent,pyridinium optionally having a substituent, or phosphonium optionallyhaving a substituent, wherein R⁷ is H or an organic group, and may bethe same or different, and any two thereof may be bonded to each otherto form a ring.

R⁷ is preferably H or a C₁₋₁₀ organic group, more preferably H or a C₁₋₄organic group, and still more preferably H or a C₁₋₄ alkyl group.

Examples of the metal atom include alkali metals (Group 1) and alkalineearth metals (Group 2), and preferred is Na, K, or Li.

M is preferably —H, a metal atom, or —NR⁷ ₄, more preferably —H, analkali metal (Group 1), an alkaline earth metal (Group 2), or —NR⁷ ₄,still more preferably —H, —Na, —K, —Li, or —NH₄, further preferably —Na,—K, or —NH₄, particularly preferably —Na or —NH₄, and most preferably—NH₄.

Y³ is preferably —COOM or —SO₃M, and more preferably —COOM.

Examples of suitable monomers represented by the general formula (5)include a fluoroallyl ether compound represented by the followingformula (5a):CX^(h) ₂═CFCF₂—O—(CF(CF₃)CF₂O)_(n5)—CF(CF₃)—Y³  (5a)wherein each X^(h) is the same, and represents F or H; n5 represents 0or an integer of 1 to 10; and Y³ is as defined above.

In the general formula (5a), n5 is preferably 0 or an integer of 1 to 5,more preferably 0, 1, or 2, and still more preferably 0 or 1 from theviewpoint of obtaining PTFE particles having a small primary particlesize. Y³ is preferably —COOM from the viewpoint of obtaining appropriatewater-solubility and surface activity, and M is preferably H or NH₄ fromthe viewpoint of being less likely to remain as impurities and improvingthe heat resistance of the resulting composition and the stretched bodyobtained from the composition.

The monomer represented by the general formula (5) is preferably amonomer (5b) represented by the following general formula (5b):CH₂═CF(—CF₂—O—Rf—Y³)  (5b)wherein Rf and Y³ are as described above.

Specific examples of the monomer represented by the general formula (5b)include a monomer represented by the following formula:

wherein Z¹ is F or CF₃; Z² and Z³ are each H or F; Z⁴ is H, F, or CF₃;p1+q1+r1 is an integer of 0 to 10; s1 is 0 or 1; t1 is an integer of 0to 5; and Y³ is as described above, with the proviso that when Z³ and Z⁴are both H, p1+q1+r1+s1 is not 0. More specifically, preferred examplesthereof include:

CH₂═CFCF₂OCH₂CF₂—Y³, CH₂═CFCF₂(CFCF₂O)CH₂CF₂Y³, CH₂═CFCF₂OCH₂CF₂CH₂—Y³,CH₂═CFCF₂O(CH₂CF₂CF₂O)CH₂CF₂CH₂—Y³, CH₂═CFCF₂OCF₂CF₂—Y³,CH₂═CFCF₂(CF₂CF₂CF₂O)CF₂CF₂—Y³, CH₂═CFCF₂OCF₂CF₂CH₂—Y³,CH₂═CFCF₂O(CF₂CF₂CF₂)CF₂CF₂CH—Y³, CH₂═CFCF₂OCF₂CF₂—Y³,CH₂═CFCF₂O(CF₂CF₂O)CF₂—Y³, CH₂═CFCF₂OCF₂CF₂CH₂—Y³,CH₂═CFCF₂O(CF₂CF₂)CF₂CH₂—Y³.

Of these, preferred are:

In the monomer represented by the general formula (5b), Y³ in theformula (5b) is preferably —COOM.

Specifically, the monomer represented by the general formula (5b) ispreferably at least one selected from the group consisting ofCH₂═CFCF₂OCF(CF₃)COOM and CH₂═CFCF₂OCF(CF₃)CF₂OCF(CF₃)COOM (wherein M isas defined above), and more preferably CH₂═CFCF₂OCF(CF₃)COOM.

The monomer represented by the general formula (5) is preferably amonomer (5c) represented by the following general formula (5c):CX²²═CFCF₂—O—(CF(CF₃)CF₂O)_(n5)—CF(CF₃)—Y³  (5c)wherein each X² is the same, and each represent F or H; n5 represents 0or an integer of 1 to 10; and Y³ is as defined above.

In the formula (5c), n5 is preferably 0 or an integer of 1 to 5, morepreferably 0, 1, or 2, and still more preferably 0 or 1 from theviewpoint of stability of the resulting aqueous dispersion. Y³ ispreferably —COOM¹ from the viewpoint of obtaining appropriatewater-solubility and stability of the aqueous dispersion, and M¹ ispreferably H or NH₄ from the viewpoint of being less likely to remain asimpurities and improving the heat resistance of the resulting moldedbody.

Examples of the perfluorovinylalkyl compound represented by the formula(5c) include CH₂═CFCF₂OCF(CF₃)COOM¹ andCH₂═CFCF₂OCF(CF₃)CF₂OCF(CF₃)COOM¹, wherein M¹ is as defined above.

Examples of the monomer represented by the general formula (5) furtherinclude a monomer represented by the following general formula (5d) anda monomer represented by the following general formula (5e):CF₂═CFCF₂—O—Rf—Y³  (5d)CF₂═CF—Rf—Y³  (5e)

wherein Rf and Y³ are as described above.

More specific examples thereof include:

In the general formula (6), each X is —H or —F. X may be both —F, or atleast one thereof may be —H. For example, one thereof may be —F and theother may be —H, or both may be —H.

In the general formula (6), Y is —H, —F, an alkyl group, or afluorine-containing alkyl group.

The alkyl group is an alkyl group free from fluorine atoms and may haveone or more carbon atoms. The alkyl group preferably has 6 or lesscarbon atoms, more preferably 4 or less carbon atoms, and still morepreferably 3 or less carbon atoms.

The fluorine-containing alkyl group is an alkyl group containing atleast one fluorine atom, and may have one or more carbon atoms. Thefluorine-containing alkyl group preferably has 6 or less carbon atoms,more preferably 4 or less carbon atoms, and still more preferably 3 orless carbon atoms.

Y is preferably —H, —F, or —CF₃, and more preferably —F.

In the general formula (6), at least one of X and Y preferably containsa fluorine atom. For example, X, Y, and Z may be —H, —F, and —F,respectively.

In the general formula (6), Rf is a fluorine-containing alkylene grouphaving 1 to 40 carbon atoms or a fluorine-containing alkylene grouphaving 2 to 100 carbon atoms and having an ether bond.

The fluorine-containing alkylene group preferably has 2 or more carbonatoms. The fluorine-containing alkylene group also preferably has 30 orless carbon atoms, more preferably 20 or less carbon atoms, and stillmore preferably 10 or less carbon atoms. Examples of thefluorine-containing alkylene group include —CF₂—, —CH₂CF₂—, —CF₂CF₂—,—CF₂CH₂—, —CF₂CF₂CH₂—, —CF(CF₃)—, —CF(CF₃)CF₂—, and —CF(CF₃)CH₂—. Thefluorine-containing alkylene group is preferably a perfluoroalkylenegroup.

The monomer represented by the general formula (6) is preferably atleast one selected from the group consisting of monomers represented bythe following general formulas (6a), (6b), (6c), and (6d):CF₂═CF—(CF₂)_(n1)—Y³  (6a)wherein n1 represents an integer of 1 to 10; Y³ represents —SO₃M¹ or—COOM¹; M¹ represents H, a metal atom, NR⁷ ₄, imidazolium optionallyhaving a substituent, pyridinium optionally having a substituent, orphosphonium optionally having a substituent; and R⁷ represents H or anorganic group;CF₂═CF—(CF₂C(CF₃)F)_(n2)—Y³  (6b)

wherein n2 represents an integer of 1 to 5, and Y³ is as defined above;CF₂═CF—O—(CFX^(i))_(n3)—Y³  (6c)

wherein X¹ represents F or CF₃; n3 represents an integer of 1 to 10; andY³ is as defined above; andCF₂═CF—O—(CF₂CFX¹O)_(n4)—CF₂CF₂—Y³  (6d)

wherein n4 represents an integer of 1 to 10; and Y³ and X¹ are asdefined above.

In the formula (6a), n1 is preferably an integer of 5 or less, and morepreferably an integer of 2 or less. Y³ is preferably —COOM¹ from theviewpoint of obtaining appropriate water-solubility and stability of theaqueous dispersion, and M¹ is preferably H or NH₄ from the viewpoint ofbeing less likely to remain as impurities and improving the heatresistance of the resulting molded body.

Examples of the perfluorovinylalkyl compound represented by the formula(6a) include CF₂═CFCF₂COOM¹, wherein M¹ is as defined above.

In the formula (6b), n2 is preferably an integer of 3 or less from theviewpoint of stability of the resulting aqueous dispersion, Y³ ispreferably —COOM¹ from the viewpoint of obtaining appropriatewater-solubility and stability of the aqueous dispersion, and M¹ ispreferably H or NH₄ from the viewpoint of being less likely to remain asimpurities and improving the heat resistance of the resulting moldedbody.

In the formula (6c), n3 is preferably an integer of 5 or less from theviewpoint of water-solubility, Y³ is preferably —COOM¹ from theviewpoint of obtaining appropriate water-solubility and stability of theaqueous dispersion, and M¹ is preferably H or NH₄ from the viewpoint ofimproving dispersion stability.

In the formula (6d), X¹ is preferably —CF₃ from the viewpoint ofstability of the aqueous dispersion, n4 is preferably an integer of 5 orless from the viewpoint of water-solubility, Y³ is preferably —COOM¹from the viewpoint of obtaining appropriate water-solubility andstability of the aqueous dispersion, and M¹ is preferably H or NH₄.

Examples of the perfluorovinyl ether compound represented by the formula(6d) include CF₂═CFOCF₂CF(CF₃)OCF₂CF₂COOM¹, wherein M¹ represents H,NH₄, or an alkali metal.

In the general formula (7), Rf is preferably a fluorine-containingalkylene group having 1 to 40 carbon atoms. In the general formula (7),at least one of X and Y preferably contains a fluorine atom.

The monomer represented by the general formula (7) is preferably atleast one selected from the group consisting of:

a monomer represented by the following general formula (7a):CF₂═CF—(CF₂)_(n1)—Y³  (7a)

wherein n1 represents an integer of 1 to 10; and Y³ is as defined above;and

a monomer represented by the following general formula (7b):CF₂═CF—(CF₂C(CF₃)F)_(n2)—Y³  (7b)

wherein n2 represents an integer of 1 to 5; and Y³ is as defined above.

Y³ is preferably —SO₃M¹ or —COOM¹, and M¹ is preferably H, a metal atom,NR⁷ ₄, imidazolium optionally having a substituent, pyridiniumoptionally having a substituent, or phosphonium optionally having asubstituent. R⁷ represents H or an organic group.

In the formula (7a), n1 is preferably an integer of 5 or less, and morepreferably an integer of 2 or less. Y³ is preferably —COOM¹ from theviewpoint of obtaining appropriate water-solubility and stability of theaqueous dispersion, and M¹ is preferably H or NH₄ from the viewpoint ofbeing less likely to remain as impurities and improving the heatresistance of the resulting molded body.

Examples of the perfluorovinylalkyl compound represented by the formula(7a) include CF₂═CFCF₂COOM¹, wherein M¹ is as defined above.

In the formula (7b), n2 is preferably an integer of 3 or less from theviewpoint of stability of the resulting aqueous dispersion, Y³ ispreferably —COOM¹ from the viewpoint of obtaining appropriatewater-solubility and stability of the aqueous dispersion, and M¹ ispreferably H or NH₄ from the viewpoint of being less likely to remain asimpurities and improving the heat resistance of the resulting moldedbody.

The content of the modifying monomer (A) is preferably in the range of0.00001 to 1.0% by mass. The lower limit thereof is more preferably0.0001% by mass, still more preferably 0.001% by mass, furtherpreferably 0.005% by mass, and particularly preferably 0.009% by mass.The upper limit thereof is preferably 0.90% by mass, more preferably0.50% by mass, still more preferably 0.40% by mass, further preferably0.30% by mass, still further preferably 0.10% by mass, and particularlypreferably 0.05% by mass.

In production of the TFE polymer, the surfactant (1) can be used withinthe use range described above for the production method of the presentinvention. The surfactant (1) may be added in any concentration withinthe range, and is usually added at a critical micelle concentration(CMC) or lower at the initiation of polymerization. Too large an amountof the surfactant added may cause generation of needle-shaped particleshaving a large aspect ratio and gelling of the aqueous dispersion,impairing the stability. The lower limit of the amount of the surfactant(1) used is preferably 0.0001% by mass, more preferably 0.001% by mass,still more preferably 0.01% by mass, and particularly preferably 0.1% bymass, based on the aqueous medium. The upper limit of the amount of thesurfactant (1) used is preferably 10% by mass, more preferably 5% bymass, still more preferably 3% by mass, and particularly preferably 2%by mass, based on the aqueous medium.

The surfactant may be added to the reaction vessel at once beforeinitiation of the polymerization, may be added at once after initiationof the polymerization, may be added in multiple portions during thepolymerization, or may be added continuously during the polymerization.

In production of the TFE polymer, the polymerization initiator used maybe an organic peroxide such as a persulfate (e.g., ammonium persulfate),disuccinic acid peroxide, or diglutaric acid peroxide alone or in theform of a mixture thereof. An organic peroxide may be used together witha reducing agent to form a redox system. During the polymerization, aradical scavenger such as hydroquinone or catechol may be added toadjust the radical concentration in the system.

The redox polymerization initiator is preferably a redox initiatorobtained by combining an oxidizing agent and a reducing agent. Examplesof the oxidizing agent include persulfates, organic peroxides, potassiumpermanganate, manganese triacetate, and ammonium cerium nitrate.Examples of the reducing agent include bromates, diimines, and oxalicacid. Examples of the persulfates include ammonium persulfate andpotassium persulfate. In order to increase the decomposition rate of theinitiator, the combination of the redox initiator may preferably containa copper salt or an iron salt. An example of the copper salt iscopper(II) sulfate and an example of the iron salt is iron(II) sulfate.

Examples of the redox initiator include potassium permanganate/oxalicacid, manganese triacetate/oxalic acid, and cerium ammoniumnitrate/oxalic acid, and potassium permanganate/oxalic acid ispreferred. In the case of using a redox initiator, either an oxidizingagent or a reducing agent may be charged into a polymerization tank inadvance, followed by adding the other continuously or intermittentlythereto to initiate the polymerization. For example, in the case ofpotassium permanganate/oxalic acid, preferably, oxalic acid is chargedinto a polymerization tank and potassium permanganate is continuouslyadded thereto.

In production of the TFE polymer, a known chain transfer agent may beused. Examples thereof include saturated hydrocarbons such as methane,ethane, propane, and butane, halogenated hydrocarbons such aschloromethane, dichloromethane, and difluoroethane, alcohols such asmethanol and ethanol, and hydrogen. The chain transfer agent ispreferably one in a gas state at a normal temperature and normalpressure.

The amount of the chain transfer agent used is usually 1 to 10,000 ppm,preferably 1 to 5,000 ppm, based on the total amount of TFE fed. Theamount used may be 1 to 1,000 ppm, or 1 to 500 ppm.

In production of the TFE polymer, a saturated hydrocarbon that issubstantially inert to the reaction, that is in a liquid state under thereaction conditions, and that has 12 or more carbon atoms may be used asa dispersion stabilizer for the reaction system in an amount of 2 to 10parts by mass based on 100 parts by mass of the aqueous medium. Ammoniumcarbonate, ammonium phosphate, or the like may be added as a buffer toadjust the pH during the reaction.

At completion of the polymerization for the TFE polymer, an aqueousdispersion having a solid concentration of 1.0 to 70% by mass and anaverage primary particle size of 50 to 500 nm can be obtained. Theaqueous dispersion contains the surfactant and the fluoropolymer. Also,the use of the surfactant allows for obtaining an aqueous dispersionhaving particles of the TFE polymer having a fine particle size as smallas 0.5 μm or smaller.

The lower limit of the solid concentration is preferably 5% by mass,more preferably 8% by mass. The upper limit thereof may be, but is notlimited to, 40% by mass or 35% by mass.

The lower limit of the average primary particle size is preferably 100nm, more preferably 150 nm. The upper limit thereof is preferably 400nm, more preferably 350 nm.

Fine powder can be produced by coagulating the aqueous dispersion. Theaqueous dispersion of the TFE polymer can be formed into fine powderthrough coagulation, washing, and drying. The resulting fine powder maybe used for various applications. Coagulation of the aqueous dispersionof the TFE polymer is usually performed by diluting the aqueousdispersion obtained by polymerization of polymer latex, for example,with water to a polymer concentration of 5 to 20% by mass, optionallyadjusting the pH to a neutral or alkaline, and stirring the polymer morevigorously than during the reaction in a vessel equipped with a stirrer.The coagulation may be performed under stirring while adding awater-soluble organic compound such as methanol or acetone, an inorganicsalt such as potassium nitrate or ammonium carbonate, or an inorganicacid such as hydrochloric acid, sulfuric acid, or nitric acid as acoagulating agent. The coagulation may be continuously performed using adevice such as an inline mixer.

From the viewpoint of productivity, the concentration of thenon-agglomerated TFE polymer in the discharge water generated by theagglomeration is preferably low, more preferably less than 0.4% by mass,and particularly preferably less than 0.3% by mass.

Pigment-containing or filler-containing TFE polymer fine powder in whichpigments and fillers are uniformly mixed can be obtained by addingpigments for coloring and various fillers for improving mechanicalproperties before or during the coagulation.

The wet powder obtained by coagulating the TFE polymer in the aqueousdispersion is usually dried by means of vacuum, high-frequency waves,hot air, or the like while keeping the wet powder in a state in whichthe wet powder is less fluidized, preferably in a stationary state.Friction between the powder particles especially at high temperatureusually has unfavorable effects on the TFE polymer in the form of finepowder. This is because the particles made of such a TFE polymer areeasily formed into fibrils even with a small shearing force and lose itsoriginal, stable particulate structure.

The drying is performed at a drying temperature of 10 to 250° C.,preferably 100 to 250° C.

The resulting fine powder of the TFE polymer is preferred for molding,and suitable applications thereof include tubes for hydraulic systems orfuel systems of aircraft or automobiles, flexible hoses for chemicals orvapors, and electric wire coating.

The aqueous dispersion of the TFE polymer obtained by the polymerizationis preferably mixed with a nonionic surfactant to stabilize and furtherconcentrate the aqueous dispersion, and then further mixed with,depending on its purpose, an organic or inorganic filler to form acomposition and used in a variety of applications. The composition, whenapplied to a metal or ceramic base material, can provide a coatingsurface having non-stickiness, a low coefficient of friction, andexcellent gloss, smoothness, abrasion resistance, weather resistance,and heat resistance, which is suitable for coating of rolls and cookingutensils and impregnation of glass cloth.

The aqueous dispersion may also be used to prepare an organosol of theTFE polymer. The organosol may contain the TFE polymer and an organicsolvent, and examples of the organic solvent include ether-basedsolvents, ketone-based solvents, alcohol-based solvents, amide-basedsolvents, ester-based solvents, aliphatic hydrocarbon-based solvents,aromatic hydrocarbon-based solvents, and halogenated hydrocarbon-basedsolvents. Preferably used are N-methyl-2-pyrrolidone anddimethylacetamide. The organosol may be prepared by the method disclosedin International Publication No. WO2012/002038, for example.

The aqueous dispersion of the TFE polymer or the fine powder of the TFEpolymer is also preferably used as a processing aid. When used as aprocessing aid, the aqueous dispersion or the fine powder is mixed witha host polymer, for example, to improve the melt strength of the hostpolymer in melt fabrication and to improve the mechanical strength,electric properties, incombustibility, anti-drop performance duringcombustion, and slidability of the resulting polymer.

The aqueous dispersion of the TFE polymer or the fine powder of the TFEpolymer is also preferably used as a binder for batteries or used fordustproof applications.

The aqueous dispersion of the TFE polymer or the fine powder of the TFEpolymer is also preferably combined with a resin other than the TFEpolymer to form a processing aid before use. The aqueous dispersion orthe fine powder is suitable as a material of the PTFEs disclosed in, forexample, Japanese Patent Laid-Open No. 11-49912, U.S. Pat. No.5,804,654, Japanese Patent Laid-Open No. 11-29679, and Japanese PatentLaid-Open No. 2003-2980. Processing aids containing the aqueousdispersion or the fine powder are not inferior in any way to theprocessing aids disclosed in the publications.

The aqueous dispersion of the TFE polymer is also preferably mixed withan aqueous dispersion of a melt-fabricable fluororesin so that thecomponents coagulate to form co-coagulated powder. The co-coagulatedpowder is suitable as a processing aid.

Examples of the melt-fabricable fluororesin include FEP, PFA, ETFE, andethylene/TFE/HFP copolymers (EFEPs), of which FEP is preferred.

The aqueous dispersion also preferably contains a melt-fabricablefluororesin. Examples of the melt-fabricable fluororesin include FEP,PFA, ETFE, and EFEP. The aqueous dispersion containing themelt-fabricable fluororesin may be used as a coating material. Themelt-fabricable fluororesin enables sufficient fusion of the TFE polymerparticles, improving the film-formability and providing the resultingfilm with gloss.

The fluorine-free resin to which the co-coagulated powder is added maybe in the form of powder, pellets, or emulsion. In order to achievesufficient mixing of the resins, the addition is preferably performed bya known method such as extrusion kneading or roll kneading under ashearing force.

The aqueous dispersion of the TFE polymer is also preferably used as adust suppression treatment agent. The dust suppression treatment agentmay be used in a method for suppressing dust from a dust-generatingsubstance by mixing the dust suppression treatment agent with thedust-generating substance and subjecting the mixture to acompression-shear action at a temperature of 20 to 200° C. to fibrillatethe TFE polymer, for example, methods disclosed in Japanese Patent No.2,827,152 and Japanese Patent No. 2,538,783.

The aqueous dispersion of the TFE polymer can suitably be used for thedust suppression treatment agent composition disclosed in InternationalPublication No. WO2007/004250, and can also suitably be used for themethod of dust suppression treatment disclosed in InternationalPublication No. WO2007/000812.

The dust suppression treatment agent is suitably used for dustsuppression treatment in the fields of building-products, soilstabilizers, solidifying materials, fertilizers, landfill ofincineration ash and harmful substances, and explosion proof equipment,cosmetics, and the like.

The aqueous dispersion of the TFE polymer is also preferably used as amaterial for producing TFE polymer fibers by a dispersion spinningmethod. The dispersion spinning method is a method in which the aqueousdispersion of the TFE polymer and an aqueous dispersion of a matrixpolymer are mixed and the mixture is extruded to form an intermediatefiber structure, and then the intermediate fiber structure is fired todecompose the matrix polymer and sinter the TFE polymer particles,thereby providing TFE polymer fibers.

The surfactant described above may be used to produce ahigh-molecular-weight PTFE. In other words, even without a conventionalfluorinated surfactant, the production method of the present inventionusing the surfactant can surprisingly produce PTFE having a molecularweight equivalent to that of PTFE obtained by a production method usingsuch a conventional fluorinated surfactant.

The high-molecular-weight PTFE powder obtained by polymerization hasstretchability and non melt processability, and is also useful as amaterial for a stretched body (porous body).

When the stretched body is in the form of a film (PTFE stretched film orPTFE porous film), the stretched body can be formed by stretching by aknown PTFE stretching method. Stretching allows easy formation offibrils of PTFE, resulting in a high-molecular-weight PTFE porous body(film) including nodes and fibers.

Preferably, roll-stretching a sheet-shaped or rod-shaped paste extrudatein an extruding direction can provide a uniaxially stretched film.

Further stretching in a transverse direction using a tenter, forexample, can provide a biaxially stretched film.

Prebaking treatment is also preferably performed before stretching.

This PTFE stretched body is a porous body having a high porosity, andcan suitably be used as a filter material for a variety ofmicrofiltration filters such as air filters and chemical filters and asupport member for polymer electrolyte films.

The PTFE stretched body is also useful as a material of products used inthe fields of textiles, of medical treatment, of electrochemistry, ofsealants, of air filters, of ventilation/internal pressure adjustment,of liquid filters, and of consumer goods.

The following provides examples of specific applications.

Electrochemical Field

Examples of the applications in this field include prepregs fordielectric materials, EMI-shielding materials, and heat conductivematerials. More specifically, examples thereof include printed circuitboards, electromagnetic interference shielding materials, insulatingheat conductive materials, and insulating materials.

Sealant Field

Examples of the applications in this field include gaskets, packings,pump diaphragms, pump tubes, and sealants for aircraft.

Air Filter Field

Examples of the applications in this field include ULPA filters (forproduction of semiconductors), HEPA filters (for hospitals and forproduction of semiconductors), cylindrical cartridge filters (forindustries), bag filters (for industries), heat-resistant bag filters(for exhaust gas treatment), heat-resistant pleated filters (for exhaustgas treatment), SINBRAN filters (for industries), catalyst filters (forexhaust gas treatment), adsorbent-attached filters (for HDD embedment),adsorbent-attached vent filters (for HDD embedment), vent filters (forHDD embedment, for example) filters for cleaners (for cleaners),general-purpose multilayer felt materials, cartridge filters for GT (forinterchangeable items for GT), and cooling filters (for housings ofelectronic devices).

Ventilation/Internal Pressure Adjustment Field

Examples of the applications in this field include materials for freezedrying such as vessels for freeze drying, ventilation materials forautomobiles for electronic circuits and lamps, applications relating tovessels such as vessel caps, protective ventilation for electronicdevices, including small devices such as tablet terminals and mobilephone terminals, and ventilation for medical treatment.

Liquid Filter Field

Examples of the applications in this field include liquid filters forsemiconductors (for production of semiconductors), hydrophilic PTFEfilters (for production of semiconductors), filters for chemicals (forchemical treatment), filters for pure water production lines (forproduction of pure water), and back-washing liquid filters (fortreatment of industrial discharge water).

Consumer Goods Field

Examples of the applications in this field include clothes, cable guides(movable wires for motorcycles), clothes for motor cyclists, cast liners(medical supporters), filters for cleaners, bagpipes (musicalinstrument), cables (signal cables for guitars, etc.), and strings (forstring instrument).

Textile Field

Examples of the applications in this field include PTFE fibers (fibermaterials), machine threads (textiles) weaving yarns (textiles), andropes.

Medical Treatment Field

Examples of the applications in this field include implants (stretchedarticles), artificial blood vessels, catheters, general surgicaloperations (tissue reinforcing materials), products for head and neck(dura mater alternatives), oral health (tissue regenerative medicine),and orthopedics (bandages).

The surfactant described above may also be used to produce alow-molecular-weight PTFE.

The low-molecular-weight PTFE may be produced by polymerization, or maybe produced by reducing the molecular weight of a high-molecular-weightPTFE obtained by polymerization by a known method (e.g., thermolysis,radiolysis).

A low-molecular-weight PTFE having a molecular weight of 600,000 or less(also referred to as PTFE micropowder) has excellent chemical stabilityand a very low surface energy, and is less likely to generate fibrils,and is therefore suitably used as an additive for improving thelubricity and the texture of the coating surface in production ofplastics, inks, cosmetics, coating materials, greases, parts of officeautomation equipment, and toners (e.g., see Japanese Patent Laid-OpenNo. 10-147617).

A low-molecular-weight PTFE may be obtained by dispersing apolymerization initiator and the surfactant in an aqueous medium in thepresence of a chain transfer agent, and then polymerizing TFE alone orTFE and a monomer copolymerizable with TFE.

In the case of using the low-molecular-weight PTFE obtained by thepolymerization in the form of powder, the powder particles may beobtained by coagulating the aqueous dispersion.

The high-molecular-weight PTFE as used herein means a nonmelt-processible and fibrillatable PTFE. The low-molecular-weight PTFEas used herein means a melt-fabricable and non-fibrillatable PTFE.

The term “non melt-processible” means a feature of polymer that the meltflow rate thereof cannot be measured at a temperature higher than thecrystal melting point in conformity with ASTM D-1238 and D-2116.

The presence or absence of the fibrillation ability can be determined by“paste extrusion”, a representative method of molding a“high-molecular-weight PTFE powder” which is a powder of a TFE polymer.Usually, the high-molecular-weight PTFE can be paste-extruded when it isfibrillatable. When a non-fired molded product obtained by pasteextrusion shows substantially no strength or elongation (for example,when it shows an elongation of 0% and is broken when stretched), it canbe regarded as non-fibrillatable.

The high-molecular-weight PTFE preferably has a standard specificgravity (SSG) of 2.130 to 2.280. The standard specific gravity isdetermined by the water replacement method in conformity with ASTM D-792using a sample molded in conformity with ASTM D4895-89. The“high-molecular-weight” as used herein means that the standard specificgravity is within the above range.

The low-molecular-weight PTFE has a complex viscosity at 380° C. of1×10² to 7×10⁵ Pa·s. The “low-molecular-weight” as used herein meansthat the complex viscosity is within the above range.

The high-molecular-weight PTFE has a complex viscosity significantlyhigher than that of the low-molecular-weight PTFE, and the complexviscosity thereof is difficult to measure accurately. The complexviscosity of the low-molecular-weight PTFE is measurable, but thelow-molecular-weight PTFE has difficulty in providing a molded articleto be used in measurement of the standard specific gravity. Thus, it isdifficult to measure its accurate standard specific gravity.Accordingly, in the present invention, the standard specific gravity isused as an index of the molecular weight of the high-molecular-weightPTFE, while the complex viscosity is used as an index of the molecularweight of the low-molecular-weight PTFE. It should be noted that thereis no known measuring method for directly specifying the molecularweight of either the high-molecular-weight PTFE or thelow-molecular-weight PTFE.

The high-molecular-weight PTFE preferably has a peak temperature of 333to 347° C., more preferably 335 to 345° C. The low-molecular-weight PTFEpreferably has a peak temperature of 322 to 333° C., more preferably 324to 332° C. The peak temperature is the temperature corresponding to themaximum value on a heat-of-fusion curve with a temperature-increasingrate of 10° C./min using a differential scanning calorimeter (DSC) for aPTFE which has never been heated up to 300° C. or higher.

Preferably, the high-molecular-weight PTFE has at least one endothermicpeak in a range of 333 to 347° C. on a heat-of-fusion curve with atemperature-increasing rate of 10° C./min using a differential scanningcalorimeter (DSC) for a PTFE which has never been heated up to 300° C.or higher, and has an enthalpy of fusion of 62 mJ/mg or higher at 290 to350° C. calculated from the heat-of-fusion curve.

The PTFE fine powder obtained by using the surfactant described abovemay also be used to produce unfired tape (green tape).

The surfactant, decomposition products and by-products of the surfactantby-produced from the surfactant, residual monomers, and the like may becollected from discharge water generated in the coagulation or thewashing and/or from off gas generated in the drying, and then purifiedto reuse the surfactant, the decomposition products and by-products ofthe surfactant by-produced by the surfactant, and the residual monomers.The collection and the purification may be performed by known methods,although not limited thereto. For example, they may be performed by themethods disclosed in National Publication of International PatentApplication No. 2011-520020.

(II) Melt-Fabricable Fluororesins

(1) In the production method of the present invention, thepolymerization for FEP is preferably performed at a polymerizationtemperature of 10 to 150° C. and a polymerization pressure of 0.3 to 6.0MpaG.

FEP preferably has a monomer composition ratio (% by mass) ofTFE:HFP=(60 to 95):(5 to 40), more preferably (85 to 92):(8 to 15). TheFEP may be modified with a perfluoro(alkyl vinyl ether) as a thirdcomponent within a range of 0.1 to 2% by mass of all monomers.

In the polymerization for FEP, the surfactant may be used within the userange of the production method of the present invention, and is usuallyadded in an amount of 0.0001 to 10% by mass based on 100% by mass of theaqueous medium.

In the polymerization for FEP, the chain transfer agent used ispreferably cyclohexane, methanol, ethanol, propanol, ethane, propane,butane, pentane, hexane, carbon tetrachloride, chloroform, methylenechloride, methyl chloride, or the like, and the pH buffer used ispreferably ammonium carbonate, disodium hydrogen phosphate, or the like.

The aqueous dispersion of FEP obtained by the production method of thepresent invention may optionally be subjected to post-treatment such asconcentration, and then the concentrate may be dried and powdered, andthe powder may be melt-extruded into pellets. The aqueous medium in theFEP aqueous dispersion may optionally contain an additive such as anonionic surfactant and may contain a water-soluble organic solvent suchas a water-soluble alcohol or may be free from a water-soluble organicsolvent.

The melt extrusion may be performed under any appropriately setextrusion conditions usually capable of providing pellets.

In the production method of the present invention, although theresulting FEP may contain an end group such as —CF₃ or —CF₂H on at leastone of the polymer main chain and a polymer side chain, it is preferredthat the content of thermally unstable groups such as —COOH, —CH₂OH,—COF, —CF═CF—, —CONH₂, or —COOCH₃ (hereinafter, referred to as an“unstable end group”) is low or absent.

The unstable end group is chemically unstable, and thus not only reducesthe heat resistance of the resin but also causes increase in theattenuation of the resulting electric wire.

The production method of the present invention is preferably performedin such a way that a polymer in which the total number of unstable endgroups and —CF₂H end groups at the completion of the polymerization is50 or less per 1×10⁶ carbon atoms is produced. The number of such groupsis more preferably less than 20, still more preferably 5 or less, per1×10⁶ carbon atoms. There may also be neither unstable end groups nor—CF₂H end groups, i.e. all end groups may be —CF₃ end groups.

The unstable end groups and the —CF₂H end groups may be fluorinated andconverted into the —CF₃ end groups and thereby stabilized. Examples ofthe fluorination method include, but not limited to, methods of exposingthe polymer to a fluorine radical source that generates fluorineradicals under fluorination conditions. Examples of the fluorine radicalsource include fluorine gas, CoF₃, AgF₂, UF₆, OF₂, N₂F₂, CF₃OF, andhalogen fluorides such as IF₅ and ClF₃. Of these, preferred is a methodof bringing a fluorination gas and the FEP obtained by the presentinvention into direct contact with each other. In order to control thereaction, the contact is preferably performed using a diluted fluorinegas having a fluorine gas concentration of 10 to 50% by mass. Thediluted fluorine gas is obtainable by diluting fluorine gas with aninert gas such as nitrogen gas or argon gas. The fluorine gas treatmentmay be performed at a temperature of 100 to 250° C. The treatmenttemperature is not limited to this range and may be appropriately set inaccordance with the situation. The fluorine gas treatment is preferablyperformed by feeding a diluted fluorine gas into the reactorcontinuously or intermittently. This fluorination may be performed ondry powder after the polymerization or on melt-extruded pellets.

The FEP obtained by the production method of the present invention hasgood moldability and is less likely to cause molding defects, as well ashas properties such as heat resistance, chemical resistance, solventresistance, insulation, and electric properties.

The FEP powder may be produced by a method of drying the FEP obtained bythe above-described production method of the present invention to powderthe FEP.

The powder may be fluorinated. The fluorinated powder may be produced bya method of feeding a fluorine gas to the powder obtained by theabove-described method for producing a powder to fluorinate the powderto obtain a fluorinated powder.

The FEP pellets may be produced by a method of pelletizing the FEPobtained by the above-described production method of the presentinvention.

The pellets may be fluorinated. The fluorinated pellets may be producedby a method of feeding a fluorine gas to the pellets obtained by theabove-described method for producing pellets to fluorinate the pelletsto obtain fluorinated pellets.

Thus, this FEP may be used in production of a variety of molded articlessuch as coating materials for electric wires, foamed electric wires,cables, and wires, tubes, films, sheets, and filaments.

(2) In the production method of the present invention, thepolymerization for a TFE/perfluoro(alkyl vinyl ether) copolymer such asPFA or MFA is usually preferably performed at a polymerizationtemperature of 10 to 100° C. and a polymerization pressure of 0.3 to 6.0MpaG.

The TFE/perfluoro(alkyl vinyl ether) copolymer preferably has a monomercomposition ratio (mol %) of TFE:perfluoro(alkyl vinyl ether)=(90 to99.7):(0.3 to 10), more preferably (97 to 99):(1 to 3). Theperfluoro(alkyl vinyl ether) used is preferably one represented by theformula: CF₂═CFORf⁴, wherein Rf⁴ is a perfluoroalkyl group having 1 to 6carbon atoms.

In the polymerization for the TFE/perfluoro(alkyl vinyl ether)copolymer, the surfactant may be used within the use range of theproduction method of the present invention, and is usually preferablyadded in an amount of 0.0001 to 10% by mass based on 100% by mass of theaqueous medium.

In the polymerization for the TFE/perfluoro(alkyl vinyl ether)copolymer, the chain transfer agent used is preferably cyclohexane,methanol, ethanol, propanol, propane, butane, pentane, hexane, carbontetrachloride, chloroform, methylene chloride, methyl chloride, methane,ethane, or the like, and the pH buffer used is preferably ammoniumcarbonate, disodium hydrogen phosphate, or the like.

The aqueous dispersion of the TFE/perfluoro(alkyl vinyl ether) copolymersuch as PFA or MFA obtained by the production method of the presentinvention may optionally be subjected to post-treatment such asconcentration, and then the concentrate may be dried and powdered, andthe powder may be melt-extruded into pellets. The aqueous medium in theaqueous dispersion may optionally contain an additive such as a nonionicsurfactant and may contain a water-soluble organic solvent such as awater-soluble alcohol or may be free from a water-soluble organicsolvent.

The melt extrusion may be performed under any appropriately setextrusion conditions usually capable of providing pellets.

In order to improve the heat resistance of the copolymer and toreinforce a chemical permeation suppression effect of a molded article,the copolymer is preferably subjected to a fluorine gas treatment.

The fluorine gas treatment is performed by bringing fluorine gas intocontact with a chemical permeation suppressant. However, since thereaction with fluorine is extremely exothermic, it is preferable todilute fluorine with an inert gas such as nitrogen. The amount offluorine in the fluorine gas/inert gas mixture is 1 to 100% by weight,preferably 10 to 25% by weight. The treatment temperature is 150 to 250°C., preferably 200 to 250° C. and the fluorine gas treatment duration is3 to 16 hours, preferably 4 to 12 hours. The fluorine gas treatment isperformed at a gas pressure in the range of 1 to 10 atm, preferablyatmospheric pressure. In the case of using a reactor at atmosphericpressure, the fluorine gas/inert gas mixture may be continuously passedthrough the reactor. This results in conversion of unstable ends of thecopolymer into —CF₃ ends, thermally stabilizing the copolymer.

The copolymer and the composition thereof may be molded by compressionmolding, transfer molding, extrusion molding, injection molding, blowmolding, or the like as in the case of conventional PFA.

Such a molding technique can provide a desired molded article. Examplesof the molded article include sheets, films, packings, round bars,square bars, pipes, tubes, round tanks, square tanks, tanks, wafercarriers, wafer boxes, beakers, filter housings, flowmeters, pumps,valves, cocks, connectors, nuts, electric wires, and heat-resistantelectric wires.

Preferred among these are tubes, pipes, tanks, connectors, and the liketo be used for a variety of chemical reaction devices, semiconductormanufacturing devices, and acidic or alkaline chemical feeding deviceseach requiring chemical impermeability.

The aqueous dispersion of a TFE/perfluoro(alkyl vinyl ether) copolymersuch as PFA or MFA may also be appropriately mixed with a nonionicsurfactant, and optionally polyethersulfone, polyamide-imide, and/orpolyimide and metal powder are dissolved or dispersed in an organicsolvent. Thereby, a primer composition can be obtained. This primercomposition may be used for a method of applying a fluororesin to ametal surface. The method includes applying the primer composition to ametal surface, applying a melt-fabricable fluororesin composition to theresulting primer layer, and firing the melt-fabricable fluororesincomposition layer together with the primer layer.

(3) In the production method of the present invention, thepolymerization for ETFE is preferably performed at a polymerizationtemperature of 10 to 100° C. and a polymerization pressure of 0.3 to 2.0MPaG.

The ETFE preferably has a monomer composition ratio (mol %) ofTFE:ethylene=(50 to 99):(50 to 1). The ETFE may be modified with a thirdmonomer within a range of 0 to 20% by mass of all monomers. Thecomposition ratio thereof is preferably TFE:ethylene:third monomer=(63to 94):(27 to 2):(1 to 10). The third monomer is preferablyperfluorobutyl ethylene, perfluorobutyl ethylene,3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-1-ene,2,3,3,4,4,5,5-heptafluoro-1-pentene (CH₂═CFCF₂CF₂CF₂H), or2-trifluoromethyl-3,3,3-trifluoropropene ((CF₃)₂C═CH₂).

In the polymerization for ETFE, the surfactant may be used within theuse range of the production method of the present invention, and isusually added in an amount of 0.0001 to 10% by mass based on 100% bymass of the aqueous medium.

In the polymerization for ETFE, the chain transfer agent used ispreferably cyclohexane, methanol, ethanol, propanol, ethane, propane,butane, pentane, hexane, carbon tetrachloride, chloroform, methylenechloride, methyl chloride, or the like.

The aqueous dispersion of ETFE obtained by the production method of thepresent invention may optionally be subjected to post-treatment such asconcentration, and then the concentrate may be dried and powdered, andthe powder may be melt-extruded into pellets. The aqueous medium in theaqueous dispersion may optionally contain an additive such as a nonionicsurfactant and may contain a water-soluble organic solvent such as awater-soluble alcohol or may be free from a water-soluble organicsolvent.

The melt extrusion may be performed under any appropriately setextrusion conditions usually capable of providing pellets.

The ETFE may be extrusion-molded into a sheet. In other words, powder orpellets of ETFE in a molten state may be continuously extruded through adie and then cooled to provide a sheet-shaped molded article. The ETFEmay be mixed with an additive.

Known additives may be incorporated as appropriate. Specific examplesthereof include ultraviolet absorbers, photostabilizers, antioxidants,infrared absorbers, flame retarders, flame-retardant fillers, organicpigments, inorganic pigments, and dyes. From the viewpoint of excellentweather resistance, inorganic additives are preferred.

The content of the additive in the ETFE sheet is preferably 20% by massor less, and particularly preferably 10% by mass or less, based on thetotal mass of the ETFE sheet.

The ETFE sheet has excellent mechanical strength and appearance, andthus can suitably be used for film materials (e.g., roof materials,ceiling materials, outer wall materials, inner wall materials, andcoating materials) of film-structured buildings (e.g., sportsfacilities, gardening facilities, and atriums).

In addition to the film materials of film-structured buildings, the ETFEsheet is also useful for, for example, outdoor boards (e.g.,noise-blocking walls, windbreak fences, breakwater fences, roof panelsof carports, shopping arcades, footpath walls, and roof materials),shatter-resistant window films, heat-resistant waterproof sheets,building materials (e.g., tent materials of warehouse tents, filmmaterials for shading, partial roof materials for skylights, windowmaterials alternative to glass, film materials for flame-retardantpartitions, curtains, outer wall reinforcement, waterproof films,anti-smoke films, non-flammable transparent partitions, roadreinforcement, interiors (e.g., lighting, wall surfaces, and blinds),exteriors (e.g., tents and signboards)), living and leisure goods (e.g.,fishing rods, rackets, golf clubs, and screens), automobile materials(e.g., hoods, damping materials, and bodies), aircraft materials,shipment materials, exteriors of home appliances, tanks, vessel innerwalls, filters, film materials for construction works, electronicmaterials (e.g., printed circuit boards, circuit boards, insulatingfilms, and release films), surface materials for solar cell modules,mirror protection materials for solar thermal energy, and surfacematerials for solar water heaters.

(4) The production method of the present invention may be used toproduce an electrolyte polymer precursor.

In the production method of the present invention, the polymerizationfor the electrolyte polymer precursor is preferably performed at apolymerization temperature of 10 to 100° C. and a polymerizationpressure of 0.1 to 2.0 MPaG. The electrolyte polymer precursor containsa vinyl ether monomer as described below and can be converted into anion-exchangeable polymer through a hydrolysis treatment.

An example of the vinyl ether monomer to be used for the electrolytepolymer precursor is

a fluoromonomer represented by the general formula (150):CF₂═CF—O—(CF₂CFY¹⁵¹—O)_(n)—(CFY¹⁵²)_(m)-A¹⁵¹

wherein Y¹⁵¹ represents a fluorine atom, a chlorine atom, a —SO₂F group,or a perfluoroalkyl group; the perfluoroalkyl group optionallycontaining ether oxygen and a —SO₂F group; n represents an integer of 0to 3; n Y¹⁵¹s are the same as or different from each other; Y¹⁵²represents a fluorine atom, a chlorine atom, or a —SO₂F group; mrepresents an integer of 1 to 5; m Y¹⁵²s are the same as or differentfrom each other; A¹⁵¹ represents —SO₂X¹⁵¹, —COZ¹⁵¹, or —POZ¹⁵²Z¹⁵³; X¹⁵¹represents F, Cl, Br, I, —OR¹⁵¹, or —NR¹⁵²R¹⁵³; Z¹⁵¹, Z¹⁵², and Z¹⁵³ arethe same as or different from each other, and each represent —NR¹⁵⁴R¹⁵⁵or —OR¹⁵⁶; and R¹⁵¹, R¹⁵², R¹⁵³, R¹⁵⁴, R¹⁵⁵, and R¹⁵⁶ are the same as ordifferent from each other, and each represent H, ammonium, an alkalimetal, or an alkyl group, aryl group, or sulfonyl-containing groupoptionally containing a fluorine atom. The electrolyte polymer precursorpreferably has a monomer composition ratio (mol %) of TFE:vinylether=(50 to 99):(50 to 1), more preferably TFE:vinyl ether=(50 to93):(50 to 7).

The electrolyte polymer precursor may be modified with a third monomerwithin a range of 0 to 20% by mass of all monomers. Examples of thethird monomer include multifunctional monomers such as CTFE, vinylidenefluoride, perfluoroalkyl vinyl ether, and divinylbenzene.

The electrolyte polymer precursor thereby obtained may be molded into afilm, followed by hydrolysis using an alkali solution and a treatmentusing a mineral acid, and thereby used as a polymer electrolyte film forfuel cells, electrolysis devices, redox flow batteries, and the like.

The electrolyte polymer precursor may be hydrolyzed using an alkalisolution while the dispersed state thereof is maintained, therebyproviding an electrolyte polymer dispersion.

This dispersion may be then heated up to 120° C. or higher in apressurized vessel and thereby dissolved in, for example, a solventmixture of water and an alcohol, i.e., converted into a solution state.

The solution thereby obtained may be used as a binder for electrodes.Also, the solution may be combined with a variety of additives and castto form a film, and the film may be used for antifouling films, organicactuators, or the like.

(5) TFE/VDF Copolymer

In the production method of the present invention, the polymerizationfor the TFE/VDF copolymer may be performed at any polymerizationtemperature, for examples, 0 to 100° C. The polymerization pressure isdetermined as appropriate in accordance with the other polymerizationconditions such as the polymerization temperature, and may be usually 0to 9.8 MPaG.

The TFE/VDF copolymer preferably has a monomer composition ratio (mol %)of TFE:VDF=(5 to 90):(95 to 10). The TFE/VDF copolymer may be modifiedwith a third monomer within a range of 0 to 50 mol % of all monomers.The composition ratio thereof is preferably TFE:ethylene:thirdmonomer=(30 to 85):(10 to 69.9):(0.1 to 10).

The third monomer is preferably a monomer represented by the formula:CX¹¹X¹²═CX¹³(CX¹⁴X¹⁵)_(n11)X¹⁶

wherein X¹¹ to X¹⁶ are the same as or different from each other, andeach represent H, F, or Cl; n11 represents an integer of 0 to 8, withthe proviso that the third monomer is other than TFE and VDF; or amonomer represented by the formula:CX²¹X²²═CX²³—O(CX²⁴X²⁵)_(n21)X²⁶

wherein X²¹ to X²⁶ are the same as or different from each other, andeach represent H, F, or Cl; and n21 represents an integer of 0 to 8.

The third monomer may be a fluorine-free ethylenic monomer. From theviewpoint of maintaining the heat resistance and the chemicalresistance, the fluorine-free ethylenic monomer is preferably selectedfrom ethylenic monomers having 6 or less carbon atoms. Examples thereofinclude ethylene, propylene, 1-butene, 2-butene, vinyl chloride,vinylidene chloride, alkyl vinyl ethers (e.g., methyl vinyl ether, ethylvinyl ether, and propyl vinyl ether), maleic acid, itaconic acid,3-butenoic acid, 4-pentenoic acid, vinylsulfonic acid, acrylic acid, andmethacrylic acid.

In the polymerization for the TFE/VDF copolymer, the surfactantdescribed above may be used within the use range of the productionmethod of the present invention, and is usually added in an amount of0.0001 to 5% by mass based on 100% by mass of the aqueous medium.

The TFE/VDF copolymer obtained by the polymerization may be amidated bybringing it into contact with a nitrogen compound capable of generatingammonia water, ammonia gas, or ammonia.

The TFE/VDF copolymer obtained by the above-described method may alsopreferably be used as a material for providing TFE/VDF copolymer fibersby a spinning-drawing method. The spinning-drawing method is a methodfor obtaining a TFE/VDF copolymer fiber by melt spinning a TFE/VDFcopolymer, cooling and solidifying it to obtain an undrawn yarn, andthen running the undrawn yarn in a heating cylinder to draw the undrawnyarn.

The TFE/VDF copolymer may be dissolved in an organic solvent to providea solution of the TFE/VDF copolymer. Examples of the organic solventinclude nitrogen-containing organic solvents such asN-methyl-2-pyrrolidone, N,N-dimethyl acetamide, and dimethyl formamide;ketone-based solvents such as acetone, methyl ethyl ketone,cyclohexanone, and methyl isobutyl ketone; ester-based solvents such asethyl acetate and butyl acetate; ether-based solvents such astetrahydrofuran and dioxane; and general-purpose organic solvents havinga low boiling point such as solvent mixtures thereof. The solution maybe used as a binder for batteries.

The aqueous dispersion of the TFE/VDF copolymer may preferably be usedto coat a porous base material formed from a polyolefin resin to providea composite porous film. The aqueous dispersion may also preferablycontain inorganic particles and/or organic particles dispersed thereinand be used to coat a porous base material to provide a composite porousfilm. The composite porous film thereby obtained may be used as aseparator for lithium secondary batteries.

The powder of the melt-fabricable fluororesin is suitably used as apowdery coating material. When applied to a base material, the powderycoating material made of the melt-fabricable fluororesin powder canprovide a film having a smooth surface. The melt-fabricable fluororesinpowder having an average particle size of 1 μm or greater and smallerthan 100 μm is particularly suitable as a powdery coating material usedfor electrostatic coating. The melt-fabricable fluororesin powder havingan average particle size of 100 μm or greater and 1,000 μm or smaller isparticularly suitable as a powdery coating material used for rotationalcoating or rotational molding.

The melt-fabricable fluororesin powder can be produced by a method ofdrying the melt-fabricable fluororesin obtained by the production methodof the present invention described above to powder the melt-fabricablefluororesin. The method for producing the melt-fabricable fluororesinpowder is also one aspect of the present invention.

(III) Fluoroelastomers

In the production method of the present invention, the polymerizationreaction for the fluoroelastomer is initiated by charging pure water andthe surfactant into a pressure-resistant reaction vessel equipped with astirrer, deoxidizing the system, charging the monomers, increasing thetemperature to a predetermined level, and adding a polymerizationinitiator. The pressure decreases as the reaction progresses, andadditional monomers are fed continuously or intermittently to maintainthe initial pressure. When the amount of the monomers fed reaches apredetermined level, feeding is stopped, and the monomers in thereaction vessel are purged and the temperature is returned to roomtemperature, whereby the reaction is completed. In this case, polymerlatex can be continuously taken out of the reaction vessel.

In particular, in the case of producing a thermoplastic elastomer as thefluoroelastomer, it is also possible to use a method in whichfluoropolymer fine particles are synthesized at a high concentrationdefined as described above and then diluted for further polymerizationas disclosed in International Publication No. WO00/01741, whereby thefinal polymerization rate can be increased as compared with ordinarypolymerization.

The polymerization for the fluoroelastomer may be performed underconditions appropriately selected from the viewpoints of physicalproperties of the target polymer and control of the polymerization rate,and is performed at a polymerization temperature of usually −20 to 200°C., preferably 5 to 150° C., and a polymerization pressure of usually0.5 to 10 MPaG, preferably 1 to 7 MPaG. The polymerization mediumpreferably has a pH usually maintained at 2.5 to 13 using a pH adjusterto be described later by a known method, for example.

Examples of the monomer used in the polymerization for thefluoroelastomer include vinylidene fluoride, as well asfluorine-containing ethylenically unsaturated monomers having fluorineatoms at least as much as the carbon atoms therein and copolymerizablewith vinylidene fluoride. Examples of the fluorine-containingethylenically unsaturated monomers include trifluoropropene,pentafluoropropene, hexafluorobutene, and octafluorobutene. Of these,hexafluoropropene is particularly preferred because of the properties ofthe elastomer obtained when hexafluoropropene blocks the crystal growthof the polymer. Examples of the fluorine-containing ethylenicallyunsaturated monomers also include trifluoroethylene, TFE, and CTFE.Fluorine-containing monomers containing one or two or more chlorineand/or bromine substituents may also be used. Perfluoro(alkyl vinylethers) such as perfluoro(methyl vinyl ether) may also be used. TFE andHFP are preferred for producing fluoroelastomer.

The fluoroelastomer preferably has a monomer composition ratio (% bymass) of vinylidene fluoride:HFP:TFE=(20 to 70):(20 to 48):(0 to 32),more preferably (20 to 70):(30 to 48):(0 to 32), and still morepreferably (32 to 64):(30 to 48):(0 to 27). The fluoroelastomer havingthis composition ratio exhibits good elastomeric characteristics,chemical resistance, and thermal stability.

In the polymerization for the fluoroelastomer, the surfactant may beused within the use range of the production method of the presentinvention, and is usually added in an amount of 0.0001 to 20% by mass,preferably 10% by mass or less, and more preferably 2% by mass or less,based on 100% by mass of the aqueous medium.

In the polymerization for the fluoroelastomer, the polymerizationinitiator used may be a known inorganic radical polymerizationinitiator. Examples of particularly useful inorganic radicalpolymerization initiators include conventionally known water-solubleinorganic peroxides, such as persulfates, perphosphates, perborates,percarbonates or permanganates of sodium, potassium, and ammonium. Theradical polymerization initiator may be further activated with areducing agent such as thiosulfate, phosphite, or hypophosphite ofsodium, potassium, or ammonium, or with an easily oxidizable metalcompound such as an iron(I) salt, a copper(I) salt, or a silver salt. Apreferred inorganic radical polymerization initiator is ammoniumpersulfate, which is more preferably used in redox systems.

The concentration of the polymerization initiator added is appropriatelydetermined in accordance with the molecular weight of the targetfluoropolymer and the polymerization reaction rate, and is set to 0.0001to 10% by mass, preferably 0.01 to 5% by mass, based on 100% by mass ofthe total amount of the monomers.

In the polymerization for the fluoroelastomer, a known chain transferagent may be used, and examples thereof include hydrocarbons, esters,ethers, alcohols, ketones, chlorine compounds, and carbonates. Ahydrocarbon, an ester, an ether, an alcohol, a chlorine compound, aniodine compound, or the like may be used as the thermoplastic elastomer,for example. Of these, preferred are acetone and isopropyl alcohol. Fromthe viewpoint of reducing a reaction rate drop in polymerization for athermoplastic elastomer, isopentane, diethyl malonate, and ethyl acetateare preferred. Diiodine compounds such as I(CF₂)₄I, I(CF₂)₆I, and ICH₂Iare preferred because they can iodize ends of the polymer and allow theresulting polymer to serve as a reactive polymer.

The amount of the chain transfer agent used is usually 0.5×10−3 to5×10−3 mol %, preferably 1.0×10−3 to 3.5×10⁻³ mol %, based on the totalamount of the monomers fed.

Paraffin wax may preferably be used as an emulsification stabilizer onthe polymerization for the fluoroelastomer, for example. A phosphate,sodium hydroxide, potassium hydroxide, or the like may preferably beused as a pH adjuster in the polymerization for a thermoplasticelastomer, for example.

At completion of the polymerization, the fluoroelastomer obtained by theproduction method of the present invention has a solid concentration of1.0 to 40% by mass, an average particle size of 0.03 to 1 μm, preferably0.05 to 0.5 μm, and a number average molecular weight of 1,000 to2,000,000.

The fluoroelastomer obtained by the production method of the presentinvention may optionally be mixed with a dispersion stabilizer such as ahydrocarbon surfactant or be concentrated, for example, to form adispersion suitable for rubber molding. The dispersion is subjected totreatments such as pH adjustment, solidification, and heating. Thetreatments are performed as follows.

The pH adjustment is performed such that a mineral acid such as nitricacid, sulfuric acid, hydrochloric acid, or phosphoric acid and/or acarboxylic acid or the like having 5 or less carbon atoms and havingpK=4.2 or lower is added to adjust the pH to 2 or lower.

The solidification is performed by adding an alkaline earth metal salt.Examples of the alkaline earth metal salt include nitrates, chlorates,and acetates of calcium or magnesium.

Although the pH adjustment and the solidification may be performed inany order, the pH adjustment is preferably performed prior to performingthe solidification.

These operations are followed by washing with the same volume of wateras the fluoroelastomer to remove a small amount of impurities such asbuffer solution and salts present in the fluoroelastomer and drying ofthe fluoroelastomer. The drying is usually performed at about 70 to 200°C. while the air is circulated in a drying furnace at high temperature.

The fluoroelastomer may be either a partially fluorinated elastomer or aperfluoroelastomer.

Examples of the partially fluorinated elastomer include vinylidenefluoride (VdF)-based fluoroelastomers, tetrafluoroethylene(TFE)/propylene (Pr)-based fluoroelastomers, tetrafluoroethylene(TFE)/propylene/vinylidene fluoride (VdF)-based fluoroelastomers,ethylene/hexafluoropropylene (HFP)-based fluoroelastomers,ethylene/hexafluoropropylene (HFP)/vinylidene fluoride (VdF)-basedfluoroelastomers, and ethylene/hexafluoropropylene(HFP)/tetrafluoroethylene (TFE)-based fluoroelastomers. Of these, thepartially fluorinated elastomer is preferably at least one selected fromthe group consisting of vinylidene fluoride-based fluoroelastomers andtetrafluoroethylene/propylene-based fluoroelastomers.

The vinylidene fluoride-based fluoroelastomer is preferably a copolymercontaining 45 to 85 mol % of vinylidene fluoride and 55 to 15 mol % ofat least one monomer copolymerizable with and different from vinylidenefluoride. The vinylidene fluoride-based fluoroelastomer is morepreferably a copolymer containing 50 to 80 mol % of vinylidene fluorideand 50 to 20 mol % of at least one monomer copolymerizable with anddifferent from vinylidene fluoride.

Examples of the at least one monomer copolymerizable with and differentfrom vinylidene fluoride include monomers such as tetrafluoroethylene(TFE), hexafluoropropylene (HFP), fluoroalkyl vinyl ethers,chlorotrifluoroethylene (CTFE), trifluoroethylene, trifluoropropylene,pentafluoropropylene, trifluorobutene, tetrafluoroisobutene,hexafluoroisobutene, vinyl fluoride, a fluoromonomer represented by thegeneral formula (100): CH₂═CFRf¹⁰¹ (wherein Rf¹⁰¹ is a linear orbranched fluoroalkyl group having 1 to 12 carbon atoms), a fluoromonomerrepresented by the general formula (170): CH₂═CH—(CF₂)_(n)—X¹⁷¹ (whereinX¹⁷¹ is H or F; and n is an integer of 3 to 10), and a monomer thatprovides a crosslinking site; and non-fluorinated monomers such asethylene, propylene, and alkyl vinyl ethers. These may be used alone orin any combination thereof. Of these, preferred is at least one selectedfrom the group consisting of TFE, HFP, fluoroalkyl vinyl ether, andCTFE. The fluoroalkyl vinyl ether is preferably a fluoromonomerrepresented by the general formula (160).

Specific examples of the vinylidene fluoride-based fluoroelastomersinclude VdF/HFP-based rubber, VdF/HFP/TFE-based rubber, VdF/CTFE-basedrubber, VdF/CTFE/TFE-based rubber, rubber based on VDF and afluoromonomer represented by the general formula (100), rubber based onVDF, a fluoromonomer represented by the general formula (100), and TFE,rubber based on VDF and perfluoro(methyl vinyl ether) (PMVE),VDF/PMVE/TFE-based rubber, and VDF/PMVE/TFE/HFP-based rubber. The rubberbased on VDF and a fluoromonomer represented by the general formula(100) is preferably VDF/CH₂═CFCF₃-based rubber. The rubber based on VDF,a fluoromonomer represented by the formula (100), and TFE is preferablyVDF/TFE/CH₂═CFCF₃-based rubber.

The VDF/CH₂═CFCF₃-based rubber is preferably a copolymer containing 40to 99.5 mol % of VDF and 0.5 to 60 mol % of CH₂═CFCF₃, more preferably acopolymer containing 50 to 85 mol % of VDF and 20 to 50 mol % ofCH₂═CFCF₃.

The tetrafluoroethylene/propylene-based fluoroelastomer is preferably acopolymer containing 45 to 70 mol % of tetrafluoroethylene, 55 to 30 mol% of propylene, and 0 to 5 mol % of a fluoromonomer that provides acrosslinking site.

The fluoroelastomer may be a perfluoroelastomer. The perfluoroelastomeris preferably at least one selected from the group consisting ofperfluoroelastomers containing TFE, such as a copolymer containing TFEand a fluoromonomer represented by the general formula (160), (130), or(140) and a copolymer containing TFE, a fluoromonomer represented by thegeneral formula (160), (130), or (140), and a monomer that provides acrosslinking site.

In the case of the TFE/PMVE copolymer, the composition ratio thereof ispreferably 45 to 90/10 to 55 (mol %), more preferably 55 to 80/20 to 45,and still more preferably 55 to 70/30 to 45.

In the case of the copolymer of TFE, PMVE, and a monomer that provides acrosslinking site, the composition ratio thereof is preferably 45 to89.9/10 to 54.9/0.01 to 4 (mol %), more preferably 55 to 77.9/20 to49.9/0.1 to 3.5, and still more preferably 55 to 69.8/30 to 44.8/0.2 to3.

In the case of the copolymer of TFE and a fluoromonomer represented bythe general formula (160), (130), or (140) having 4 to 12 carbon atoms,the composition ratio thereof is preferably 50 to 90/10 to 50 (mol %),more preferably 60 to 88/12 to 40, and still more preferably 65 to 85/15to 35.

In the case of the copolymer of TFE, a fluoromonomer represented by thegeneral formula (160), (130), or (140) having 4 to 12 carbon atoms, anda monomer that provides a crosslinking site, the composition ratiothereof is preferably 50 to 89.9/10 to 49.9/0.01 to 4 (mol %), morepreferably 60 to 87.9/12 to 39.9/0.1 to 3.5, and still more preferably65 to 84.8/15 to 34.8/0.2 to 3.

When these copolymers have compositional features outside these ranges,the properties as a rubber elastic body are lost, and the propertiestend to be close to those of a resin.

The perfluoroelastomer is preferably at least one selected from thegroup consisting of copolymers of TFE, a fluoromonomer represented bythe general formula (140), and a fluoromonomer that provides acrosslinking site, copolymers of TFE and a perfluorovinyl etherrepresented by the general formula (140), copolymers of TFE and afluoromonomer represented by the general formula (160), and copolymersof TFE, a fluoromonomer represented by the general formula (160), and amonomer that provides a crosslinking site.

Examples of the perfluoroelastomer further include theperfluoroelastomers disclosed in documents such as InternationalPublication No. WO97/24381, Japanese Patent Publication No. 61-57324,Japanese Patent Publication No. 04-81608, and Japanese PatentPublication No. 05-13961.

From the viewpoint of achieving an excellent compression set at hightemperature, the fluoroelastomer preferably has a glass transitiontemperature of −70° C. or higher, more preferably −60° C. or higher, andstill more preferably −50° C. or higher. From the viewpoint of achievinggood cold resistance, the glass transition temperature is preferably 5°C. or lower, more preferably 0° C. or lower, and still more preferably−3° C. or lower.

The glass transition temperature can be determined as follows.Specifically, using a differential scanning calorimeter (DSC822e,manufactured by Mettler-Toledo International Inc.), 10 mg of a sample isheated at a rate of 10° C./min to give a DSC curve, and the temperatureis read at the midpoint of two intersections between each of theextension lines of the base lines before and after the secondarytransition of the DSC curve and the tangent line at the inflection pointof the DSC curve.

From the viewpoint of achieving good heat resistance, thefluoroelastomer preferably has a Mooney viscosity ML(1+20) at 170° C. of30 or higher, more preferably 40 or higher, and still more preferably 50or higher. From the viewpoint of achieving good processability, theMooney viscosity is preferably 150 or lower, more preferably 120 orlower, and still more preferably 110 or lower.

From the viewpoint of achieving good heat resistance, thefluoroelastomer preferably has a Mooney viscosity ML(1+20) at 140° C. of30 or higher, more preferably 40 or higher, and still more preferably 50or higher. From the viewpoint of achieving good processability, theMooney viscosity is preferably 180 or lower, more preferably 150 orlower, and still more preferably 110 or lower.

From the viewpoint of achieving good heat resistance, thefluoroelastomer preferably has a Mooney viscosity ML(1+10) at 100° C. of10 or higher, more preferably 20 or higher, and still more preferably 30or higher. From the viewpoint of achieving good processability, theMooney viscosity is preferably 120 or lower, more preferably 100 orlower, and still more preferably 80 or lower.

The Mooney viscosity can be determined using a Mooney viscometer MV2000Emanufactured by Alpha Technologies Inc. at 170° C., 140° C., or 100° C.in conformity with JIS K 6300.

The fluoroelastomer obtained by the production method of the presentinvention may be in any form as long as it is obtainable by thepolymerization. The fluoroelastomer may be in the form of an aqueousdispersion as polymerized, or may be used in the form of a gum or acrumb obtained by conventionally known coagulation, drying, and anyother treatment on the aqueous dispersion as polymerized. The surfactantused in the production method of the present invention can improve thestability of the aqueous dispersion, and is more preferably used in apolymerization method in which substances insoluble in water such as aninitiator, including an organic peroxide, and a chain transfer agent,including an iodine or bromine compound, are added during thepolymerization defined as described above.

The gum is a small particulate mass of the fluoroelastomer. The crumb isan amorphous mass of the fluoroelastomer resulting from fusion ofparticles that cannot maintain the form of small particles as gum atroom temperature.

The fluoroelastomer may be mixed with an additive such as a curing agentand a filler to be processed into a fluoroelastomer composition.

Examples of the curing agent include polyols, polyamines, organicperoxides, organotins, bis(aminophenol)tetraamine, andbis(thioaminophenol).

The fluoroelastomer composition is made of the above fluoroelastomer,and thus is substantially free from an emulsifier and is excellent inthat it is easily crosslinked during molding.

The fluoroelastomer may be molded to form a fluoroelastomer molded body.The molding may be performed by any method such as a known method usingthe above-mentioned curing agent.

The fluoroelastomer molded body is suitable for seals, gaskets, electricwire coatings, hoses, tubes, laminated products, and accessories,particularly parts for semiconductor manufacturing devices andautomobile parts.

The polymerization usually provides an aqueous dispersion containing thefluoropolymer. The fluoropolymer is usually at a concentration of 8 to50% by mass in the aqueous dispersion obtained by the polymerization. Inthe aqueous dispersion, the lower limit of the concentration of thefluoropolymer is preferably 10% by mass, more preferably 15% by mass,while the upper limit thereof is preferably 40% by mass, more preferably35% by mass.

The aqueous dispersion obtained by the polymerization may beconcentrated or subjected to dispersion stabilization treatment to forma dispersion, or may be subjected to coagulation or agglomeration, andcollected and dried into powder or other solid.

The surfactant may also be suitably used as a dispersant for dispersingthe fluoropolymer obtained by the polymerization in an aqueous medium.

The polymerization usually provides an aqueous dispersion containingparticles of the fluoropolymer, the surfactant, and the aqueous medium.The aqueous dispersion contains particles of the fluoropolymer dispersedin an aqueous medium in the presence of the surfactant.

The surfactant (1) is preferably 0.0001 to 15% by mass based on theaqueous dispersion. When the amount of the surfactant (1) is less than0.0001% by mass, the dispersion stability may deteriorate, and when theamount thereof is more than 15% by mass, dispersion effects commensuratewith the amount thereof may not be obtained, which is impractical. Thelower limit of the surfactant (1) is more preferably 0.001% by mass,while the upper limit thereof is more preferably 10% by mass, still morepreferably 2% by mass.

The aqueous dispersion may be any of an aqueous dispersion obtained bythe polymerization, a dispersion obtained by concentrating this aqueousdispersion or subjecting the aqueous dispersion to dispersionstabilization treatment, and an aqueous dispersion obtained bydispersing powder of the fluoropolymer into an aqueous medium in thepresence of the surfactant.

The aqueous dispersion may also be produced as a purified aqueousdispersion by a method including a step (I) of bringing the aqueousdispersion obtained by the polymerization into contact with an anionexchange resin or a mixed bed containing an anion exchange resin and acation exchange resin in the presence of a nonionic surfactant (I),and/or a step (II) of concentrating the aqueous dispersion obtained bythis step such that the solid concentration is 30 to 70% by mass basedon 100% by mass of the aqueous dispersion (II).

The nonionic surfactant may be, but is not limited to, any of those tobe described later. The anion exchange resin to be used may be, but isnot limited to, a known one. The contact with the anion exchange resinmay be performed by a known method.

A method for producing the aqueous dispersion may include subjecting theaqueous dispersion obtained by the polymerization to the step (I), andsubjecting the aqueous dispersion obtained in the step (I) to the step(II) to produce a purified aqueous dispersion. The step (II) may also becarried out without carrying out the step (I) to produce a purifiedaqueous dispersion.

Further, the step (I) and the step (II) may be repeated or combined.

Examples of the anion exchange resin include known ones such as astrongly basic anion exchange resin containing as a functional group a—N⁺X⁻(CH₃)₃ group (wherein X represents Cl or OH) or a strongly basicanion exchange resin containing a —N⁺X⁻(CH₃)₃(C₂H₄OH) group (wherein Xis as described above). Specific examples thereof include thosedescribed in International Publication No. WO99/62858, InternationalPublication No. WO03/020836, International Publication No.WO2004/078836, International Publication No. WO2013/027850, andInternational Publication No. WO2014/084399.

Examples of the cation exchange resin include, but are not limited to,known ones such as a strongly acidic cation exchange resin containing asa functional group a —SO₃ ⁻ group and a weakly acidic cation exchangeresin containing as a functional group a —COO— group. Of these, from theviewpoint of removal efficiency, a strongly acidic cation exchange resinis preferred, a H⁺ form strongly acidic cation exchange resin is morepreferred.

The “mixed bed containing a cation exchange resin and an anion exchangeresin” encompasses, but is not limited to, those in which the resins arefilled into a single column, those in which the resins are filled intodifferent columns, and those in which the resins are dispersed in anaqueous dispersion.

The concentration may be carried out by a known method. Specificexamples include those described in International Publication No.WO2007/046482 and International Publication No. WO2014/084399.

Examples thereof include phase separation, centrifugal sedimentation,cloud point concentration, electric concentration, electrophoresis,filtration treatment using ultrafiltration, filtration treatment using areverse osmosis membrane (RO membrane), and nanofiltration treatment.The concentration may concentrate the fluoropolymer concentration to be30 to 70% by mass in accordance with the application thereof. Theconcentration may impair the stability of the dispersion. In such acase, a dispersion stabilizer may be further added.

The dispersion stabilizer added may be the aforementioned nonionicsurfactant or any of other various surfactants.

The nonionic surfactant is the same as the nonionic surfactantexemplified as the nucleating agent described above, and can beappropriately selected from the nonionic surfactants described above.

Also, the cloud point of the nonionic surfactant is a measure of itssolubility in water. The surfactant used in the aqueous dispersion has acloud point of about 30° C. to about 90° C., preferably about 35° C. toabout 85° C.

The total amount of the dispersion stabilizer is 0.5 to 20% by mass interms of concentration, based on the solid of the dispersion. When theamount of the dispersion stabilizer is less than 0.5% by mass, thedispersion stability may deteriorate, and when the amount thereof ismore than 20% by mass, dispersion effects commensurate with the amountthereof may not be obtained, which is impractical. The lower limit ofthe amount of the dispersion stabilizer is more preferably 2% by mass,while the upper limit thereof is more preferably 12% by mass.

The surfactant may be removed by the concentration operation.

The aqueous dispersion obtained by the polymerization may also besubjected to a dispersion stabilization treatment without concentrationdepending on the application, to prepare an aqueous dispersion having along pot life. Examples of the dispersion stabilizer used include thesame as those described above.

Examples of the applications of the aqueous dispersion include, but arenot limited to, those in which the aqueous dispersion is directly used,such as coating achieved by applying the aqueous dispersion to a basematerial, drying the dispersion, and optionally firing the workpiece;impregnation achieved by impregnating a porous support such as nonwovenfabric or a resin molded article with the aqueous dispersion, drying thedispersion, and preferably firing the workpiece; and casting achieved byapplying the aqueous dispersion to a base material such as glass, dryingthe dispersion, optionally immersing the workpiece into water to removethe base material and to thereby provide a thin film. Examples of suchapplications include aqueous dispersion-type coating materials, tentmembranes, conveyor belts, binders for electrodes, and water repellentsfor electrodes.

The aqueous dispersion may be used in the form of an aqueous coatingmaterial for coating by mixing with a known compounding agent such as apigment, a thickener, a dispersant, a defoaming agent, an antifreezingagent, a film-forming aid, or by compounding another polymer compound.

In addition, the aqueous dispersion may be used for additiveapplications, for example, for a binder application for preventing theactive material of an electrode from falling off, or for a compoundapplication such as a drip inhibitor.

For the purpose of adjusting the viscosity of the aqueous dispersion orimproving the miscibility with a pigment or filler, the aqueousdispersion may preferably contain an anionic surfactant. The anionicsurfactant may be appropriately added to an extent that causes noproblems from the economic and environmental viewpoints.

Examples of the anionic surfactant include non-fluorinated anionicsurfactants and fluorine-containing anionic surfactants. Preferred arefluorine-free, non-fluorinated anionic surfactants, i.e., hydrocarbonanion surfactants.

For the purpose of adjusting the viscosity, any known anionicsurfactants may be used, for example, anionic surfactants disclosed inInternational Publication No. WO2013/146950 and InternationalPublication No. WO2013/146947. Examples thereof include those having asaturated or unsaturated aliphatic chain having 6 to 40 carbon atoms,preferably 8 to 20 carbon atoms, and more preferably 9 to 13 carbonatoms. The saturated or unsaturated aliphatic chain may be either linearor branched, or may have a cyclic structure. The hydrocarbon may havearomaticity, or may have an aromatic group. The hydrocarbon may containa hetero atom such as oxygen, nitrogen, or sulfur.

Examples of the anionic surfactants include alkyl sulfonates, alkylsulfates, and alkyl aryl sulfates, and salts thereof; aliphatic(carboxylic) acids and salts thereof; and phosphoric acid alkyl estersand phosphoric acid alkyl aryl esters, and salts thereof. Of these,preferred are alkyl sulfonates, alkyl sulfates, and aliphatic carboxylicacids, or salts thereof.

Preferred examples of the alkyl sulfates or salts thereof includeammonium lauryl sulfate and sodium lauryl sulfate.

Preferred examples of the aliphatic carboxylic acids or salts thereofinclude succinic acid, decanoic acid, undecanoic acid, undecenoic acid,lauric acid, hydrododecanoic acid, or salts thereof.

The amount of the anionic surfactant added depends on the types of theanion surfactant and other compounding agents, and is preferably 10 ppmto 5,000 ppm based on the mass of the solid of the fluoropolymer.

The lower limit of the amount of the anionic surfactant added is morepreferably 50 ppm or more, still more preferably 100 ppm or more. Toosmall an amount of the anionic surfactant may result in a poor viscosityadjusting effect.

The upper limit of the amount of the anionic surfactant added is morepreferably 3,000 ppm or less, still more preferably 2,000 ppm or less.Too large an amount of the anionic surfactant may impair mechanicalstability and storage stability of the aqueous dispersion.

For the purpose of adjusting the viscosity of the aqueous dispersion,components other than the anionic surfactants, such as methyl cellulose,alumina sol, polyvinyl alcohol, and carboxylated vinyl polymers may alsobe added.

For the purpose of adjusting the pH of the aqueous dispersion, a pHadjuster such as aqueous ammonia may also be added.

The aqueous dispersion may optionally contain other water solublepolymer compounds to an extent that does not impair the characteristicsof the aqueous dispersion.

Examples of the other water soluble polymer compound include, but arenot limited to, polyethylene oxide (dispersion stabilizer), polyethyleneglycol (dispersion stabilizer), polyvinylpyrrolidone (dispersionstabilizer), phenol resin, urea resin, epoxy resin, melamine resin,polyester resin, polyether resin, silicone acrylic resin, siliconeresin, silicone polyester resin, and polyurethane resin. The aqueousdispersion may further contain a preservative, such asisothiazolone-based, azole-based, pronopol, chlorothalonil,methylsulfonyltetrachloropyridine, carbendazim, fluorfolpet, sodiumdiacetate, and diiodomethylparatolylsulfone.

The surfactant, decomposition products and by-products of the surfactantby-produced by the surfactant, and residual monomers may be collectedfrom discharge water generated in the coagulation or the washing and/orfrom off gas generated in the drying, and then purified to reuse thesurfactant, the decomposition products and by-products of thesurfactant, and the residual monomers by-produced by the surfactant. Thecollection and the purification may be performed by known methods,although not limited thereto. For example, they may be performed by themethods disclosed in National Publication of International PatentApplication No. 2011-520020.

The collection of the surfactant, the decomposition products andby-products of the surfactant by-produced by the surfactant, theresidual monomers, and the like from discharge water generated in thecoagulation, discharge water generated in the washing, and off gasgenerated in the drying and the purification thereof may be performed byany known methods, although not limited thereto, such as the methodsdisclosed in U.S. Patent Application Publication No. 2007/15937, U.S.Patent Application Publication No. 2007/25902, and U.S. PatentApplication Publication No. 2007/27251. Specific examples of the methodsare as follows.

An example of the method of collecting the surfactant, the decompositionproducts and by-products of the surfactant by-produced by thesurfactant, the residual monomers, and the like from discharge water isa method in which the discharge water is brought into contact withadsorbent particles formed of ion exchange resin, activated carbon,silica gel, clay, zeolite, or the like, so that the particles areallowed to adsorb the surfactant and the others, and then the dischargewater and the adsorbent particles are separated. Incinerating theadsorbent particles having adsorbed the surfactant and the others canprevent emission of the surfactant and the others into the environment.

Alternatively, the surfactant and the others may be removed and elutedby a known method from the ion exchange resin particles having adsorbedthe surfactant and the others, and collected. For example, in the caseof using anion exchange resin particles as the ion exchange resinparticles, the surfactant and the others can be eluted by bringing amineral acid into contact with an anion exchange resin. When awater-soluble organic solvent is added to the resulting eluate, themixture is usually separated into two phases. Since the lower phasecontains the surfactant and the others, it is possible to collect thesurfactant and the others by collecting and neutralizing the lowerphase. Examples of the water-soluble organic solvent include polarsolvents such as alcohols, ketones, and ethers.

Other methods of collecting the surfactant and the others from ionexchange resin particles include a method of using an ammonium salt anda water-soluble organic solvent and a method of using an alcohol and, ifnecessary, an acid. In the latter method, ester derivatives of thesurfactant and the others are generated, and they can easily beseparated from the alcohol by distillation.

When the discharge water contains fluoropolymer particles and othersolids, they are preferably removed before the discharge water and theadsorbent particles are brought into contact with each other. Examplesof methods of removing the fluoropolymer particles and other solidsinclude a method of adding an aluminum salt, for example, to depositthese components, and then separating the discharge water and thedeposits, and an electrocoagulation method. The components may also beremoved by a mechanical method, and examples thereof include a crossflowfiltration method, a depth filtration method, and a precoat filtrationmethod.

From the viewpoint of productivity, the discharge water preferablycontains the fluoropolymer in a non-agglomerated form in a lowconcentration, more preferably less than 0.4% by mass, and particularlypreferably less than 0.3% by mass.

An example of the method of collecting the surfactant and the othersfrom the off gas is a method in which a scrubber is brought into contactwith deionized water, an alkaline aqueous solution, an organic solventsuch as a glycol ether solvent, or the like to provide a scrubbersolution containing the surfactant and the others. When the alkalineaqueous solution used is a highly concentrated alkaline aqueoussolution, the scrubber solution can be collected in a state where thesurfactant and the others are phase-separated, and thus the surfactantand the others can be easily collected and reused. Examples of thealkali compound include alkali metal hydroxides and quaternary ammoniumsalts.

The scrubber solution containing the surfactant and the others may beconcentrated using a reverse osmosis membrane, for example. Theconcentrated scrubber solution usually contains fluoride ions. Still,the fluoride ions may be removed by adding alumina after theconcentration so that the surfactant and the others can easily bereused. Alternatively, the scrubber solution may be brought into contactwith adsorbent particles so that the adsorbent particles can adsorb thesurfactant and the others, and thereby the surfactant and the others maybe collected by the aforementioned method.

The surfactant and the others collected by any of the methods may bereused in the production of fluoropolymer.

The present invention also relates to a surfactant for polymerizationrepresented by the following general formula (1):

wherein R¹ to R⁵ each represent H or a monovalent substituent, with theproviso that at least one of R¹ and R³ represents a group represented bythe general formula: —Y—R⁶ and at least one of R² and R⁵ represents agroup represented by the general formula: —X-A or a group represented bythe general formula: —Y—R⁶;

X is the same or different at each occurrence and represents a divalentlinking group or a direct bond;

A is the same or different at each occurrence and represents —COOM,—SO₃M, or —OSO₃M, wherein M is H, a metal atom, NR⁷ ₄, imidazoliumoptionally having a substituent, pyridinium optionally having asubstituent, or phosphonium optionally having a substituent, wherein R⁷is H or an organic group;

Y is the same or different at each occurrence and represents a divalentlinking group selected from the group consisting of —S(═O)₂—, —O—,—COO—, —OCO—, —CONR⁸—, and —NR⁸CO—, or a direct bond, wherein R⁸ is H oran organic group;

R⁶ is the same or different at each occurrence and represents an alkylgroup having 2 or more carbon atoms and optionally containing, betweencarbon atoms, at least one selected from the group consisting of acarbonyl group, an ester group, an amide group, and a sulfonyl group;and

any two of R¹ to R⁵ optionally bind to each other to form a ring.

The surfactant for polymerization can suitably be used as the surfactantused in the production method of the present invention. A preferredconstitution of the surfactant for polymerization is the same as that ofthe surfactant used in the production method of the present invention.

The present invention also relates to use of a surfactant for productionof a fluoropolymer by polymerizing a fluoromonomer in an aqueous medium,the surfactant being represented by the following general formula (1):

wherein R¹ to R⁵ each represent H or a monovalent substituent, with theproviso that at least one of R¹ and R³ represents a group represented bythe general formula: —Y—R⁶ and at least one of R² and R⁵ represents agroup represented by the general formula: —X-A or a group represented bythe general formula: —Y—R⁶;

X is the same or different at each occurrence and represents a divalentlinking group or a direct bond;

A is the same or different at each occurrence and represents —COOM,—SO₃M, or —OSO₃M, wherein M is H, a metal atom, NR⁷ ₄, imidazoliumoptionally having a substituent, pyridinium optionally having asubstituent, or phosphonium optionally having a substituent, wherein R⁷is H or an organic group;

Y is the same or different at each occurrence and represents a divalentlinking group selected from the group consisting of —S(═O)₂—, —O—,—COO—, —OCO—, —CONR⁸—, and —NR⁸CO—, or a direct bond, wherein R⁸ is H oran organic group;

R⁶ is the same or different at each occurrence and represents an alkylgroup having 2 or more carbon atoms and optionally containing, betweencarbon atoms, at least one selected from the group consisting of acarbonyl group, an ester group, an amide group, and a sulfonyl group;and

any two of R¹ to R⁵ optionally bind to each other to form a ring.

The aqueous medium, the fluoromonomer, and the fluoropolymer arepreferably the same as those to be used in the production method of thepresent invention. A preferred constitution of the surfactant is thesame as that of the surfactant used in the production method of thepresent invention.

The present invention also relates to a composition comprising afluoropolymer and a surfactant represented by the following generalformula (1):

wherein R¹ to R⁵ each represent H or a monovalent substituent, with theproviso that at least one of R¹ and R³ represents a group represented bythe general formula: —Y—R⁶ and at least one of R² and R⁵ represents agroup represented by the general formula: —X-A or a group represented bythe general formula: —Y—R⁶;

X is the same or different at each occurrence and represents a divalentlinking group or a direct bond;

A is the same or different at each occurrence and represents —COOM,—SO₃M, or —OSO₃M, wherein M is H, a metal atom, NR⁷ ₄, imidazoliumoptionally having a substituent, pyridinium optionally having asubstituent, or phosphonium optionally having a substituent, wherein R⁷is H or an organic group;

Y is the same or different at each occurrence and represents a divalentlinking group selected from the group consisting of —S(═O)₂—, —O—,—COO—, —OCO—, —CONR⁸—, and —NR⁸CO—, or a direct bond, wherein R⁸ is H oran organic group;

R⁶ is the same or different at each occurrence and represents an alkylgroup having 2 or more carbon atoms and optionally containing, betweencarbon atoms, at least one selected from the group consisting of acarbonyl group, an ester group, an amide group, and a sulfonyl group;and

any two of R¹ to R⁵ optionally bind to each other to form a ring.

The fluoropolymer is preferably the same as that to be used in theproduction method of the present invention, more preferably afluororesin, still more preferably a fluororesin having a fluorinesubstitution percentage described above of 50% or higher, furtherpreferably a fluororesin having the fluorine substitution percentage ofhigher than 50%, still further preferably a fluororesin having thefluorine substitution percentage of 55% or higher, yet furtherpreferably a fluororesin having the fluorine substitution percentage of60% or higher, particularly preferably a fluororesin having the fluorinesubstitution percentage of 75% or higher, particularly more preferably afluororesin having the fluorine substitution percentage of 80% orhigher, and most preferably a fluororesin having the fluorinesubstitution percentage of 90 to 100%, i.e., a perfluororesin.

The perfluororesin is more preferably a fluororesin having the fluorinesubstitution percentage of 95 to 100%, still more preferably PTFE, FEP,or PFA, and particularly preferably PTFE.

A preferred constitution of the surfactant is the same as that of thesurfactant used in the production method of the present invention.

The composition of the present invention may be in the form of anaqueous dispersion, powder, or pellets. The aqueous dispersion may be adispersion as polymerized, or may be one obtained by processing thedispersion as polymerized. For example, a nonionic surfactant or thelike may be added to the aqueous dispersion for mechanical stability andstorage stability. The amount of the nonionic surfactant added ispreferably 0.5 to 25% by mass based on the fluoropolymer. The lowerlimit of the addition amount is more preferably 1% by mass, still morepreferably 3% by mass. The upper limit thereof is more preferably 20% bymass, still more preferably 15% by mass, and particularly preferably 10%by mass.

The aqueous dispersion is a dispersion system in which an aqueous mediumserves as a dispersion medium and the fluoropolymer serves as adispersoid. The aqueous medium may be any liquid containing water, andmay contain, in addition to water, an organic solvent such as analcohol, an ether, a ketone, or paraffin wax.

The lower limit value of the content of the surfactant in thecomposition is preferably 10 ppb, more preferably 100 ppb, still morepreferably 1 ppm, further preferably 10 ppm, and particularly preferably50 ppm, based on the fluoropolymer. The upper limit value thereof ispreferably 100,000 ppm, more preferably 50,000 ppm, still morepreferably 10,000 ppm, and particularly preferably 5,000 ppm, based onthe fluoropolymer.

In the composition of the present invention, the fluoropolymer ispreferably one obtained by polymerization using a hydrocarbonsurfactant.

The composition of the present invention may contain a hydrocarbonsurfactant. Examples of the hydrocarbon surfactant include theaforementioned surfactant (1).

The composition may further contain conventionally known additives suchas pigments and fillers in addition to the fluoropolymer and thehydrocarbon surfactant. The additives may be used to an extent that doesnot inhibit the effects of the present invention.

The composition of the present invention may be produced by using acarboxylic acid-based surfactant or by combining a carboxylic acid-basedsurfactant with a specific polymerization initiator.

Examples of the carboxylic acid-based surfactants include thesurfactants (1) described above in which A is —COOM.

Examples of the specific polymerization initiator include water-solubleradical polymerization initiators and redox initiators.

The water-soluble radical polymerization initiator may be a knownwater-soluble peroxide, and examples thereof include ammonium salts,potassium salts, and sodium salts of persulfuric acid and percarbonicacid, t-butyl permaleate, and t-butyl hydroperoxide, and the use amountthereof may be 0.1 to 20 times that of peroxide.

For example, in a case where the polymerization is performed at a lowtemperature of 30° C. or lower, the polymerization initiator used ispreferably a redox initiator obtained by combining an oxidizing agentand a reducing agent. Examples of the oxidizing agent includepersulfates, organic peroxides, potassium permanganate, manganesetriacetate, and ammonium cerium nitrate. Examples of the reducing agentinclude bromates, diimines, and oxalic acid. Examples of the persulfatesinclude ammonium persulfate and potassium persulfate. In order toincrease the decomposition rate of the initiator, the combination of theredox initiator may preferably contain a copper salt or an iron salt. Anexample of the copper salt is copper(II) sulfate and an example of theiron salt is iron(II) sulfate.

Examples of the redox initiator include potassium permanganate/oxalicacid, manganese triacetate/oxalic acid, cerium ammonium nitrate/oxalicacid, and bromates, and potassium permanganate/oxalic acid is preferred.In the case of using a redox initiator, either an oxidizing agent or areducing agent may be charged into a polymerization tank in advance,followed by adding the other continuously or intermittently thereto toinitiate the polymerization. For example, in the case of using potassiumpermanganate/oxalic acid, preferably, oxalic acid is charged into apolymerization tank and potassium permanganate is continuously addedthereto.

The composition of the present invention is preferably substantiallyfree from a fluorine-containing surfactant. In the composition of thepresent invention, the term “substantially free from fluorine-containingsurfactant” means that the fluorine-containing surfactant is 10 ppm orless based on the fluoropolymer. The content of the fluorine-containingsurfactant is preferably 1 ppm or less, more preferably 100 ppb or less,still more preferably 10 ppb or less, further preferably 1 ppb or less,and particularly preferably the fluorine-containing surfactant is belowthe detection limit as measured by liquid chromatography-massspectrometry (LC/MS/MS).

The amount of the fluorine-containing surfactant can be determined by aknown method. For example, it can be determined by LC/MS/MS analysis.First, any of the obtained aqueous dispersion, the powder, the moldedbody, the pellets, a fluoropolymer obtained by refining the molded body,or a fluoropolymer obtained by refining the pellets is extracted into anorganic solvent of methanol, and the extracted liquid is subjected toLC/MS/MS analysis. Then, the molecular weight information is extractedfrom the LC/MS/MS spectrum to confirm agreement with the structuralformula of the candidate surfactant.

Thereafter, aqueous solutions having five or more differentconcentration levels of the confirmed surfactant are prepared, andLC/MS/MS analysis is performed for each concentration level to prepare acalibration curve with the area.

The obtained aqueous dispersion, powder, or powder obtained by crushinga molded body is subjected to Soxhlet extraction with methanol, and theextracted liquid is subjected to LC/MS/MS analysis for quantitativemeasurement.

The fluorine-containing surfactant is the same as those exemplified inthe production method of the present invention. For example, thesurfactant may be a fluorine atom-containing surfactant having, in theportion excluding the anionic group, 20 or less carbon atoms in total,may be a fluorine-containing surfactant having an anionic moiety havinga molecular weight of 800 or less, and may be a fluorine-containingsurfactant having a Log POW of 3.5 or less.

Examples of the anionic fluorine-containing surfactant include compoundsrepresented by the general formula (N⁰), and specific examples thereofinclude compounds represented by the general formula (N¹), compoundsrepresented by the general formula (N²), compounds represented by thegeneral formula (N³), compounds represented by the general formula (N⁴),and compounds represented by the general formula (N⁵). More specificexamples thereof include a perfluorocarboxylic acid (I) represented bythe general formula (I), an ω-H perfluorocarboxylic acid (II)represented by the general formula (II), a perfluoropolyethercarboxylicacid (III) represented by the general formula (III), aperfluoroalkylalkylenecarboxylic acid (IV) represented by the generalformula (IV), a perfluoroalkoxyfluorocarboxylic acid (V) represented bythe general formula (V), a perfluoroalkylsulfonic acid (VI) representedby the general formula (VI), an ω-H perfluorosulfonic acid (VII)represented by the general formula (VII), a perfluoroalkylalkylenesulfonic acid (VIII) represented by the general formula (VIII), analkylalkylene carboxylic acid (IX) represented by the general formula(IX), a fluorocarboxylic acid (X) represented by the general formula(X), an alkoxyfluorosulfonic acid (XI) represented by the generalformula (XI), and a compound (XII) represented by the general formula(XII).

The present invention also relates to a molded body comprising thecomposition. The molded body is preferably a stretched body. Examples ofthe stretched body include, but are not limited to, yarns, tubes, tapes,and films (e.g., uniaxially stretched films and biaxially stretchedfilms).

The composition of the present invention can also be produced bypreparing the fluoropolymer by the method for producing a fluoropolymerdescribed above and then treating the fluoropolymer by theabove-described method or the like.

EXAMPLES

The present invention is described with reference to Examples, but thepresent invention is not intended to be limited by these Examples.

The parameters in the Examples were determined by the following methods.

Average Primary Particle Size

The average primary particle size was determined by dynamic lightscattering. A fluoropolymer aqueous dispersion with the fluoropolymersolid concentration being adjusted to about 1.0% by mass was prepared.The average primary particle size was determined from 70 measurementprocesses using ELSZ-1000S (manufactured by Otsuka Electronics Co.,Ltd.) at 25° C. The refractive index of the solvent (water) was 1.3328and the viscosity of the solvent (water) was 0.8878 mPa-s.

Standard specific gravity (SSG) Using a sample molded in conformity withASTM D4895-89, the SSG was determined by the water replacement method inconformity with ASTM D-792.

Mooney viscosity (ML1+20 (170° C.))

The Mooney viscosity can be determined using a Mooney viscometer MV2000Emanufactured by Alpha Technologies Inc. at 170° C. in conformity withJIS K 6300.

In Example 4 described later, CH₂═CF(CF₂OCF(CF₃)CF₂OCF(CF₃)COONH₄) wasused as the modifying monomer A.

Synthesis Example 1

5-methoxy-5-oxopentanoic acid (25.0 g) and a catalytic amount of DMFwere added to a reactor, and thionyl chloride (40.7 g) was dropwiseadded thereto at room temperature using a dropping funnel. Aftercompletion of stirring, 0,0′-(1,4-dichloro-1,4-dioxobutane-2,3-diyl)dimethyl diglutarate was synthesized in a yield of 90% using anevaporator.

Next, O,O′-(1,4-dichloro-1,4-dioxobutane-2,3-diyl) dimethyl diglutarate(5.22 g), tartaric acid (2.38 g), and sulfuric acid were added using thereactor, and the mixture was stirred at 70° C. After the stirring, themixture was purified to obtain2,3-bis((5-methoxy-5-oxopentanoyl)oxy)succinic acid as the targetproduct in a yield of 52%.

Next, MeOH was added to 2,3-bis((5-methoxy-5-oxopentanoyl)oxy)succinicacid (3.23 g) in the reactor, and the mixture was stirred, and 2 M NH₃in MeOH (7.95 mL) was dropwise added thereto at room temperature.

After stirring, the product was dried to obtain the target ammonium salt(hereinafter, referred to as surfactant A) in a yield of 90%.

Synthesis Example 2

Tartaric acid (19.1 g) and MeOH were added to a reactor, and the mixturewas stirred. Thionyl chloride (79.1 g) was added dropwise thereto atroom temperature. After completion of stirring, the solvent wasdistilled off to obtain dimethyl tartrate in a yield of 93%.

Next, dimethyl tartrate (4.0 g), succinic anhydride (4.49 g), andpyridine (3.54 g) were added to the reactor and stirred at 100° C. Then,after stirring, toluene was added thereto, and the solid precipitate wascollected by filtration. Thereafter, vacuum drying was performed toobtain4,4′-((1,4-dimethoxy-1,4-dioxobutane-2,3-diyl)bis(oxy))bis(4-oxobutanoicacid) (hereinafter, referred to as surfactant B) in a yield of 86%.

Synthesis Example 3

A 2,3-bis((6-methoxy-6-oxohexanoyl)oxy)succinic acid ammonium salt(hereinafter, referred to as surfactant C) was synthesized in the samemanner as in Synthesis Example 1, except that 6-methoxy-6-oxohexanoicacid was used instead of 5-methoxy-5-oxopentanoic acid.

Example 1

To a glass autoclave with an internal volume of 1 L, 550 g of deionizeddegassed water, 30 g of paraffin wax, and 0.1465 g of the surfactant Awere added. The reactor was sealed and the system was purged withnitrogen, so that oxygen was removed. The reactor was heated up to 70°C. and TFE was charged into the reactor such that the reactor wasadjusted to 0.78 MPa. Then, 0.011 g of ammonium persulfate (APS) servingas a polymerization initiator was charged thereinto. TFE was charged soas to keep the reaction pressure constant at 0.78 MPa. When 50 g of TFEwas charged, the stirring was stopped and the pressure was releaseduntil the reactor was adjusted to the atmospheric pressure. The aqueousdispersion was collected from the reactor and cooled so that theparaffin wax was separated. The particles contained in the resultingPTFE aqueous dispersion had an average primary particle size of 228 nm.The solid content in the resulting PTFE aqueous dispersion was 8.2% bymass.

The resulting PTFE aqueous dispersion was dried at 150° C. for 18 hours.

The SSG of the resulting PTFE resin was determined to be 2.190. Thisdemonstrates that the resulting PTFE was a high-molecular-weight PTFE.

Example 2

To a glass autoclave with an internal volume of 1 L, 550 g of deionizeddegassed water, 30 g of paraffin wax, and 0.126 g of the surfactant Bwere added. The reactor was sealed and the system was purged withnitrogen, so that oxygen was removed. The reactor was heated up to 70°C. and TFE was charged into the reactor such that the reactor wasadjusted to 0.78 MPa. Then, 0.011 g of ammonium persulfate (APS) servingas a polymerization initiator was charged thereinto. TFE was charged soas to keep the reaction pressure constant at 0.78 MPa. During thereaction, 0.504 g of the surfactant B was added. When 50 g of TFE wascharged, the stirring was stopped and the pressure was released untilthe reactor was adjusted to the atmospheric pressure. The aqueousdispersion was collected from the reactor and cooled so that theparaffin wax was separated. The particles contained in the resultingPTFE aqueous dispersion had an average primary particle size of 236 nm.The solid content in the resulting PTFE aqueous dispersion was 8.2% bymass.

The resulting PTFE aqueous dispersion was dried at 150° C. for 18 hours.

The SSG of the resulting PTFE resin was determined to be 2.194. Thisdemonstrates that the resulting PTFE was a high-molecular-weight PTFE.

Example 3

To a glass autoclave with an internal volume of 1 L, 550 g of deionizeddegassed water, 30 g of paraffin wax, and 0.0312 g of the surfactant Cwere added. The reactor was sealed and the system was purged withnitrogen, so that oxygen was removed. The reactor was heated up to 70°C. and TFE was charged into the reactor such that the reactor wasadjusted to 0.78 MPa. Then, 0.011 g of ammonium persulfate (APS) servingas a polymerization initiator was charged thereinto. TFE was charged soas to keep the reaction pressure constant at 0.78 MPa. When 50 g of TFEwas charged, the stirring was stopped and the pressure was releaseduntil the reactor was adjusted to the atmospheric pressure. The aqueousdispersion was collected from the reactor and cooled so that theparaffin wax was separated. The particles contained in the resultingPTFE aqueous dispersion had an average primary particle size of 233 nm.The solid content in the resulting PTFE aqueous dispersion was 8.2% bymass.

The resulting PTFE aqueous dispersion was dried at 150° C. for 18 hours.

The SSG of the resulting PTFE resin was determined to be 2.200. Thisdemonstrates that the resulting PTFE was a high-molecular-weight PTFE.

Example 4

To a reactor made of SUS with an internal volume of 6 L and equippedwith a stirrer, 3,600 g of deionized degassed water, 180 g of paraffinwax, and 0.540 g of the surfactant A were added. The reactor was sealedand the system was purged with nitrogen, so that oxygen was removed. Thereactor was heated up to 70° C. and TFE was charged into the reactorsuch that the reactor was adjusted to 2.70 MPa. At the same time that0.360 g of modifying monomer A was charged into the reactor, 0.620 g ofammonium persulfate (APS) and 1.488 g of disuccinic acid peroxide (DSP)were charged as polymerization initiators. TFE was charged so as to keepthe reaction pressure constant at 2.70 MPa. At the same time as TFE wasstarted to be charged, an aqueous solution of surfactant A adjusted to aconcentration of 10% by mass was started to be continuously charged.When 890 g of TFE was charged, the stirring was stopped and the pressurewas released until the reactor was adjusted to the atmospheric pressure.By the end of the reaction, 156.6 g of the surfactant A aqueous solutionadjusted to a concentration of 10% by mass was charged.

The content was collected from the reactor and cooled so that theparaffin wax was separated. The particles contained in the resultingPTFE aqueous dispersion had an average primary particle size of 198 nm.

The solid content in the resulting PTFE aqueous dispersion was 19.1% bymass.

The resulting aqueous dispersion of PTFE was diluted with deionizedwater to have a solid content of about 10% by mass and coagulated undera high-speed stirring condition. After separating the water, thecoagulated wet powder was dried at 150° C. for 18 hours.

The SSG of the resulting PTFE resin was determined to be 2.233. Thisdemonstrates that the resulting PTFE was a high-molecular-weight PTFE.

Example 5

To an autoclave made of SUS with an internal volume of 3 L, 1,500 g ofdeionized water and 0.300 g of the surfactant A were added. The reactorwas sealed and the system was purged with nitrogen to remove oxygen. Thetemperature of the reactor was raised to 80° C., and while stirring, amonomer composition (initial monomer) consisting of vinylidene fluoride(VDF)/tetrafluoroethylene (TFE)/hexafluoropropylene (HFP) (=19/11/70 mol%) was fed under pressure until the pressure reaches 1.53 MPa. Then, apolymerization initiator aqueous solution prepared by dissolving 0.030 gof ammonium persulfate (APS) in deionized water was fed under nitrogengas pressure to initiate the reaction. At the point when the internalpressure dropped to 1.50 MPa as the polymerization proceeded, a mixedmonomer consisting of VDF/TFE/HFP (=50/20/30 mol %) was charged untilthe internal pressure was kept constant at 1.53 MPa. 90 minutes and 180minutes after the start of polymerization, 0.06 g and 0.03 g APS weredissolved in deionized water and fed under nitrogen gas pressure asdescribed above to continue the polymerization reaction. When 502 g ofthe mixed monomer was added, the stirring was stopped and the pressurewas released until the reactor was adjusted to the atmospheric pressure.The autoclave was cooled to obtain an aqueous dispersion having a solidconcentration of 20.5% by mass.

An aqueous aluminum sulfate solution was added to the aqueous dispersionto cause coagulation. The resulting coagulated product was washed withwater and dried to obtain a rubbery fluorine-containing copolymer. TheMooney viscosity of the rubbery fluorine-containing copolymer was ML1+20(170° C.)=74.5. The copolymer compositional features were determined byNMR analysis to be VDF/TFE/HFP=50/20/30 (mol %).

The invention claimed is:
 1. A method for producing a fluoropolymercomprising: polymerizing a fluoromonomer in an aqueous medium in thepresence of a surfactant to provide a fluoropolymer, the surfactantbeing a compound represented by the following general formula (1-1) or acompound represented by the general formula (1-2):

wherein R³ to R⁵ each represent H or a monovalent substituent; X is thesame or different at each occurrence and represents a direct bond or adivalent linking group containing at least one selected from the groupconsisting of a carbonyl group, an ester group, an amide group, and asulfonyl group; A is the same or different at each occurrence andrepresents —COOM, —SO₃M, or —OSO₃M, wherein M is H, a metal atom, NR⁷ ₄,imidazolium optionally having a substituent, pyridinium optionallyhaving a substituent, or phosphonium optionally having a substituent,wherein R⁷ is H or an organic group; the group represented by theformula: —Y—R⁶ is the same or different at each occurrence andrepresents a group represented by the formula: —R¹⁰—CO—R¹¹, a grouprepresented by the formula: —OCO—R¹⁰—CO—R¹¹, a group represented by theformula: —COO—R¹⁰—CO—R¹¹, a group represented by the formula:—OCO—R¹⁰—COO—R¹¹, a group represented by the formula: —COO—R¹¹, a grouprepresented by the formula: —NR⁸CO—R¹⁰—CO—R¹¹, or a group represented bythe formula: —CONR⁸—R¹⁰—NR⁸CO—R¹¹, wherein R⁸ is H or an organic group;R¹⁰ is an alkylene group; and R¹¹ is an alkyl group optionally having asubstituent; and any two of R³ to R⁵ optionally bind to each other toform a ring; and if —Y—R⁶ is —COO—R¹¹, then X is a divalent linkinggroup containing at least one selected from the group consisting of acarbonyl group, an ester group, an amide group, and a sulfonyl group. 2.The method according to claim 1, wherein R⁴ and R⁵ are each H or a C₁₋₄alkyl group.
 3. The method according to claim 1, wherein M is H, Na, K,Li, or NH₄.
 4. The method according to claim 1, wherein M is Na, K, orNH₄.
 5. The method according to claim 1, wherein M is NH₄.
 6. The methodaccording to claim 1, wherein the polymerization of the fluoromonomer isperformed in the absence of a fluorine-containing surfactant.